CN113921777A - Tellurium selenium-polyaniline composite material, electrochemical preparation method thereof and application of tellurium selenium-polyaniline composite material in aspect of energy storage - Google Patents
Tellurium selenium-polyaniline composite material, electrochemical preparation method thereof and application of tellurium selenium-polyaniline composite material in aspect of energy storage Download PDFInfo
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- CN113921777A CN113921777A CN202111004309.4A CN202111004309A CN113921777A CN 113921777 A CN113921777 A CN 113921777A CN 202111004309 A CN202111004309 A CN 202111004309A CN 113921777 A CN113921777 A CN 113921777A
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 115
- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 229910052714 tellurium Inorganic materials 0.000 title claims abstract description 30
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000004146 energy storage Methods 0.000 title claims abstract description 24
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000137 annealing Methods 0.000 claims abstract description 16
- 229910001370 Se alloy Inorganic materials 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000002848 electrochemical method Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229940075397 calomel Drugs 0.000 claims abstract description 5
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000007774 positive electrode material Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 28
- 230000008569 process Effects 0.000 abstract description 17
- 239000007772 electrode material Substances 0.000 abstract description 16
- 239000011669 selenium Substances 0.000 description 63
- 239000000463 material Substances 0.000 description 51
- 229910052711 selenium Inorganic materials 0.000 description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 22
- 229910052744 lithium Inorganic materials 0.000 description 22
- 229940091258 selenium supplement Drugs 0.000 description 15
- 239000002002 slurry Substances 0.000 description 15
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- 230000000694 effects Effects 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
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- 238000010438 heat treatment Methods 0.000 description 9
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000011056 performance test Methods 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052798 chalcogen Inorganic materials 0.000 description 2
- 150000001787 chalcogens Chemical class 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- GKWAQTFPHUTRMG-UHFFFAOYSA-N lithium telluride Chemical compound [Li][Te][Li] GKWAQTFPHUTRMG-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
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- 230000001590 oxidative effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- PMYDPQQPEAYXKD-UHFFFAOYSA-N 3-hydroxy-n-naphthalen-2-ylnaphthalene-2-carboxamide Chemical compound C1=CC=CC2=CC(NC(=O)C3=CC4=CC=CC=C4C=C3O)=CC=C21 PMYDPQQPEAYXKD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002983 Li2MnO3 Inorganic materials 0.000 description 1
- 229910007346 Li2Te Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910013191 LiMO2 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012154 double-distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- ZVSWQJGHNTUXDX-UHFFFAOYSA-N lambda1-selanyllithium Chemical compound [Se].[Li] ZVSWQJGHNTUXDX-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229960001881 sodium selenate Drugs 0.000 description 1
- 239000011655 sodium selenate Substances 0.000 description 1
- 235000018716 sodium selenate Nutrition 0.000 description 1
- 229960001471 sodium selenite Drugs 0.000 description 1
- 239000011781 sodium selenite Substances 0.000 description 1
- 235000015921 sodium selenite Nutrition 0.000 description 1
- VOADVZVYWFSHSM-UHFFFAOYSA-L sodium tellurite Chemical compound [Na+].[Na+].[O-][Te]([O-])=O VOADVZVYWFSHSM-UHFFFAOYSA-L 0.000 description 1
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- 238000005406 washing Methods 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
- H01M4/362—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
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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 relates to a tellurium-selenium-polyaniline composite material, an electrochemical preparation method thereof and application in the aspect of energy storage, wherein the preparation method comprises the following steps: s1: tellurium powder and selenium powder are used as raw materials, are ground, mixed uniformly and then are packaged in vacuum, and a tellurium-selenium alloy rod is synthesized through high-temperature annealing; s2: dissolving aniline solution in alkali liquor to prepare alkaline electrolyte containing aniline solution; s3: and (3) preparing the tellurium-selenium-polyaniline composite material by taking the prepared tellurium-selenium alloy rod as a working electrode, a calomel electrode as a reference electrode and a Pt wire as a counter electrode in the prepared alkaline electrolyte containing the aniline through a constant voltage electrochemical method. The tellurium selenium-polyaniline composite material is prepared by a three-electrode constant voltage electrochemical method through specific process steps and selection and combination of process parameters, has excellent energy storage property, can be prepared into an electrode material, is applied to the aspect of energy storage, and has good application prospect and industrialization potential.
Description
Technical Field
The invention belongs to the field of inorganic semiconductor materials and energy materials, and particularly relates to a tellurium-selenium-polyaniline composite material, an electrochemical preparation method thereof and application thereof in energy storage.
Background
Lithium ion batteries, which are typical representatives of secondary batteries, have become the most widely studied commercial batteries due to their advantages of high energy density, high charge-discharge efficiency, long service life, environmental friendliness, and the like. At present, lithium ion batteries are widely applied in the fields of electronic products, electric automobiles, aerospace, aviation and the like. The most studied lithium ion batteries currently are ternary lithium batteries, such as: LiNi1/3Co1/3Mn1/3O2、Li2MnO3·LiMO2The theoretical capacity is 184mA · h · g-1、290mA·h·g-1. The lithium ion battery that has been commercialized is LiCoO2a/C, theoretical energy density of 387 W.h.kg only-1And the requirement of the electric automobile for long-distance running is difficult to meet. Therefore, it is important to develop a new lithium battery energy storage system with high energy density, long cycle life, low cost and environmental friendliness.
Chalcogen has a high capacity and energy density as a positive electrode material of a lithium battery, and thus is considered as one of the most potential candidate materials for the next generation of rechargeable lithium batteries. Lithium-sulfur (Li-S) batteries have the advantages of high sulfur reserves and low cost; however, sulfur has a fatal disadvantage that polysulfide is generated during the reaction, resulting in a shuttle effect, which greatly affects the performance of the battery. Theoretical mass capacity of lithium selenium (Li-Se) batteryAlthough the amount is only 675mA · h · g-1Compared with the theoretical mass capacity of Li-S (1672 mA. h.g)-1) Lower, but significantly higher, selenium density compared to sulfur, and volumetric capacity of Li-Se cells is comparable to that of Li-S cells (Li-Se: 3253 mA.h.cm-3，Li-S：3467mA·h·cm-3) And the conductivity of selenium is much higher than that of sulfur (Se: 1X 10-3S·m-1S is 5X 10-28S·m-1) Selenium is also considered to be one of the ideal lithium battery cathode materials. The theoretical mass capacity of tellurium element is only 429 mA.h.g-1However, the theoretical volume capacity is 2621mA · h · cm-3The energy density is 823.2 W.h.kg-1And the electric conductivity of tellurium element is 2X 102S·m-1Much higher than sulfur (5X 10)-28S·m-1) And selenium (1X 10)-3S·m-1) The method is helpful for improving the reaction kinetics in the charging and discharging processes of the battery, but the volume expansion of the Li-Te battery causes that the Li-Te battery is temporarily difficult to realize the commercial popularization.
Therefore, combining the advantages of Te and Se to form TexSeyComposite materials are one of the effective ways to inhibit the shuttling effect and volume expansion of materials. However, Te and Se have insufficient crystal lattices, are easily propped by lithium ions in the lithium intercalation process, cause volume expansion, and have a shuttle effect caused by dissolution of polyselenide. Therefore, atoms are inserted into the chalcogen element crystal lattice, the crystal lattice parameters are enlarged, chemical bonds are formed, the reaction mechanism of the self charge and discharge process of the active substance is changed, and the synergistic effect of inhibiting the volume expansion and the shuttle effect is achieved. In addition, TexSeyThe surface of the composite material is coated with the carbon material, so that the conductivity of the material can be obviously enhanced, and the energy storage performance of the battery material can be effectively enhanced. Based on the method, the tellurium selenium-polyaniline composite material is synthesized by an electrochemical method, and the application of the tellurium selenium-polyaniline composite material in the aspect of energy storage is tested.
In recent years, tellurium-selenium co-doped composite materials with photoelectric response, excellent metal ion storage capability and high electrochemical stability have been reported, and particularly, the tellurium-selenium co-doped composite materials are rarely applied to energy storage, photoelectric response and other applications, for example:
CN109748250A discloses a preparation method of a tellurium-selenium nano material, which comprises the following steps: adding sodium tellurite, sodium selenite and a morphology control material polyvinylpyrrolidone into double distilled water, fully mixing, adjusting the pH value to 9.4, adding a reducing agent hydrazine hydrate (25 wt/%) into the obtained solution reaction kettle, sealing, reacting at 180 ℃ for 24 hours, cooling, and centrifuging to obtain the two-dimensional tellurium-selenium nano material. The material has the advantages of obvious photo-thermal effect, high chemical stability, low toxicity, abundant raw materials, low price and simple preparation method. But in the preparation process, hydrazine hydrate and other solvents are used, so that certain potential safety hazard exists.
CN108394873B discloses a preparation method of a tellurium-selenium-cadmium material, which comprises the following steps: mixing a certain amount of tellurium powder, cadmium powder and selenium powder according to a molar ratio of 9:10:1, and adding into a homogenizer for homogenizing for 1 h; filling the mixed and homogenized material into a graphite cylinder, then putting the graphite cylinder into a quartz tube, then filling the quartz tube into a vacuum tube sealing furnace, vacuumizing the vacuum tube sealing furnace, and sealing the quartz tube; then the quartz tube with the sealed tube is put into a heating furnace, the heating furnace is heated up to 1200 ℃ at the heating rate of 10 ℃/min, and the temperature is kept for 3 h; and after the heat preservation is finished, stopping heating, opening the hearth, naturally cooling, and discharging at the temperature lower than 60 ℃ to obtain the tellurium-selenium-cadmium block. The preparation method of the material has low requirements on equipment, high product yield, simple process, large-scale production and low production cost, but a large amount of cadmium powder is used in the preparation method, so that certain potential safety hazard exists in the production process, and the material has certain harm to the environment.
CN107501830A discloses a preparation method of an erbium tellurium selenium composite base flexible piezoelectric film, which comprises the following steps: compounding aniline, erbium nitrate, lithium telluride, sodium selenate and cellulose, oxidizing at high temperature to obtain a composite metal oxide, dispersing the composite metal oxide in a polymethyl methacrylate/silane coupling agent/acetone solution, and then using a film throwing machine to form a film, and annealing to obtain the erbium tellurium selenium composite base flexible piezoelectric film. The preparation method of the material has better technical effect, the piezoelectric coefficient of the prepared flexible piezoelectric film is 703pC/N which is more than 7 times of that of the conventional composite piezoelectric material, but a large amount of organic solvent is used in the preparation process, so that the pollution is greatly influenced, the process is complex, and the production is not easy.
CN112310282A discloses a preparation method of a two-dimensional narrow bandgap bismuth tellurium selenium material, which comprises the following steps: etching Si substrate with hydrofluoric acid, and oxidizing at 600 deg.C in high-temperature annealing furnace to grow SiO2Layer, then pulsed laser deposition of Bi on the material2Te2.7Se0.3And finally, sputtering the Pd electrode layer by a magnetron sputtering technology. The material has good performance in a multifunctional device for efficient information storage and processing, is a resistive random access memory with good storage performance, low energy consumption and wider application prospect, and opens up a new way for the development of miniaturization of the device.
CN109616634A discloses a TexSeySzThe preparation method of the lithium secondary battery anode material comprises the following steps: through a simple one-step heat treatment method, under the space confinement effect of the porous carbon carrier, single sulfur, selenium and/or tellurium are mutually dissolved to form TexSeySzSolid solution, and uniformly loaded into the carbon support framework. The material is prepared by one-step heat treatment, the process is simple, and the complicated operation of multi-step heat treatment is avoided, but the regulation and control of the content of the obtained substances are difficult to realize in the mutual dissolving process of preparing various materials of the material.
As described above, many prior arts disclose tellurium-selenium co-doped tellurium-selenium composite materials, in which other metal elements (such as Cd, Bi, Er, Pd, etc.) are often introduced, and a large amount of other metal salts are introduced, so that the obtained tellurium-selenium composite materials have better photo-thermal effect, piezoelectric effect, energy storage application, and the like. In addition, the synthesis process of the material is complex, the synthesis conditions are strict, the large-scale production is difficult, and in addition, the electrochemical performance of the material needs to be further improved.
For the reasons, it is still very important to develop a green and environment-friendly cathode material containing two or more S-group elements, which has a relatively simple process and excellent electrochemical properties, and it is a hot spot of research in the field of lithium batteries, which is the foundation and the power of the present invention.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a tellurium-selenium-polyaniline composite material, an electrochemical preparation method thereof and application in energy storage. The method for preparing the tellurium-selenium-polyaniline composite material by adopting constant-voltage electrochemistry is simple, rapid, economic and environment-friendly, and the prepared tellurium-selenium-polyaniline composite material has the advantages of regularity and controllable morphology, and has application potential and industrial value in the direction of energy storage performance.
The first invention aims to provide an electrochemical preparation method of a tellurium-selenium-polyaniline composite material.
In order to realize the purpose, the technical scheme comprises the following steps:
s1: tellurium powder and selenium powder are used as raw materials, are ground, mixed uniformly and then are packaged in vacuum, and a tellurium-selenium alloy rod is synthesized through high-temperature annealing;
s2: dissolving aniline solution in alkali liquor to prepare alkaline electrolyte containing aniline solution;
s3: and (3) taking the tellurium-selenium alloy rod prepared in the step (S1) as a working electrode, taking a calomel electrode as a reference electrode and taking a Pt wire as a counter electrode, and preparing the tellurium-selenium-polyaniline composite material in alkaline electrolyte containing aniline solution prepared in the step (S2) by a constant voltage electrochemical method.
In step S1, the tellurium powder and the selenium powder are mixed, where the mixing mass ratio is 1-40:1, and may be, for example, 1:1, 5:1, 10:1, 20:1, 30:1, or 40: 1.
In the electrochemical preparation method of the tellurium-selenium-polyaniline composite material, in step S1, the high temperature annealing treatment temperature is 400-; the annealing time is 2 to 36 hours, and may be, for example, 2 hours, 6 hours, 12 hours, 18 hours, 24 hours, or 36 hours, and most preferably 12 hours.
In the electrochemical preparation method of the tellurium-selenium-polyaniline composite material, in step S1, the heating rate in the high-temperature annealing treatment is 1-9 ℃ for min-1For example, it may be 1 ℃ min-1、3℃min-1、5℃min-1、7℃min-1Or 9 ℃ min-1Most preferably 5 ℃ min-1。
In the electrochemical preparation method of the tellurium-selenium-polyaniline composite material, in step S2, the drying temperature of the tellurium-selenium alloy rod is 60-120 ℃, for example, 60 ℃, 80 ℃, 100 ℃ or 120 ℃; the drying time is 4 to 12 hours, and may be, for example, 4 hours, 6 hours, 8 hours, 10 hours, or 12 hours.
In the electrochemical preparation method of the tellurium-selenium-polyaniline composite material, in step S2, the alkali solution is one of a sodium hydroxide aqueous solution, a sodium carbonate aqueous solution, a sodium bicarbonate aqueous solution, a sodium acetate aqueous solution and ammonia water, and is most preferably a sodium hydroxide aqueous solution.
In the electrochemical preparation method of the tellurium-selenium-polyaniline composite material, in step S2, the concentration of the alkali liquor is 0-2mol L-1For example, it may be 0mol L-1、0.5mol L-1、1.0mol L-1、1.5mol L-1Or 2.0mol L-1Most preferably 0.5mol L-1。
In the electrochemical preparation method of the tellurium-selenium-polyaniline composite material, in step S2, the aniline concentration is 0-0.4mol L-1For example, it may be 0mol L-1、0.05mol L-1、0.10mol L-1、0.15mol L-1、0.20mol L-1、0.25mol L-1、0.3mol L-1、0.35mol L-1Or 0.4mol L-1Most preferably 0.25mol L-1。
In the electrochemical preparation method of the tellurium-selenium-polyaniline composite material of the present invention, in step S3, the voltage of the constant voltage method of the three-electrode system may be set to 0.1-3.0V, for example, 0.2V, 0.5V, 0.8V, 1.1V, 1.4V, 1.7V, 2.0V, 2.3V, 2.6V, or 2.9V; the reaction time is 1 to 96 hours, and may be, for example, 3 hours, 6 hours, 12 hours, 24 hours, 48 hours, 72 hours, or 96 hours.
In summary, in the step S3, the tellurium-selenium-polyaniline composite material prepared by the constant-voltage electrochemistry of the three-electrode system is obtained by assembling the tellurium-selenium alloy rod synthesized by high-temperature annealing in the step S1 and other electrodes into the three-electrode system, and reacting the three-electrode system with the alkaline electrolyte solution system prepared in the step S2 and containing aniline solution under certain voltage and time conditions.
The second purpose of the invention is to provide a tellurium-selenium-polyaniline composite material, and the tellurium-selenium-polyaniline composite material is marked as TexSey@PANI。
The present inventors have found that when such a preparation method is adopted, a tellurium-selenium-polyaniline composite material having a specific appearance (surface rod-like structure) can be obtained, and the surface of the tellurium-selenium-polyaniline composite material is coated with a polymer, and when certain process parameters such as the raw material dosage ratio, the voltage power, the reaction time and the like are changed, the composite material having such a form cannot be obtained.
The third invention aims to provide the energy storage application of the tellurium-selenium-polyaniline composite material, and the tellurium-selenium-polyaniline composite material is used as the positive electrode material of the battery material through the selection and combination of specific process steps and process parameters, and has good application prospect and industrialization potential. The tellurium selenium-polyaniline composite material is used as a positive electrode material of a battery.
The application scheme is as follows:
a. preparing the obtained tellurium-selenium-polyaniline composite material into a tellurium-selenium-polyaniline positive electrode material sheet of the button cell;
b: and assembling the button cell with the tellurium selenium-polyaniline positive electrode material sheet as a positive electrode material and Li as a negative electrode material, and performing energy storage application.
The step a is further set as follows:
a-1: fully grinding the tellurium-selenium-polyaniline composite material, a conductive agent and a binder in a certain proportion until the particles are uniform;
a-2: dripping a solvent into the mixture of the a-1, and fully stirring at normal temperature to physically mix the sample into uniform slurry;
a-3: transferring the uniform slurry a-2 to an aluminum foil, uniformly coating the aluminum foil by a coating machine to obtain a pole piece material, and transferring the pole piece material to a vacuum drying oven for drying;
a-4: and c, cutting the pole piece material dried in the step a-3 into a wafer, and then carrying out vacuum drying.
The step b is further set as follows:
b-1: selecting a proper button battery shell and a diaphragm, taking the pole piece material of a-4 as a positive pole piece, taking a lithium piece as a counter electrode and electrolyte with a proper formula;
b-2: sequentially stacking and assembling the materials b-1 in a glove box, and compacting the button cell by using a tablet press;
b-3: and (4) standing and activating the button cell obtained in the step (b-2), and then carrying out electrochemical performance test and energy storage application.
Specifically, the method comprises the following steps:
mixing TexSeyThe @ PANI composite material, acetylene black and PVDF are mixed to form positive electrode material slurry, the slurry is coated and dried to form a positive electrode material sheet, and then the positive electrode material sheet, the CR 2025 button battery case and the Celgard 2400 diaphragm are assembled into the button battery by the counter electrode lithium sheet.
The step a is further set as follows:
a-1: taking positive electrode material TexSey@ PANI 100mg, conductive agent acetylene black 21.4mg, binder PVDF (polyvinylidene fluoride) 21.4mg, fully grinding until the particles are uniform, and transferring to a weighing bottle;
a-2: dropping 600-1000 μ L NMP (N-methyl pyrrolidone) into the mixture by using a liquid transfer gun, stirring for 24h at normal temperature and 600r min-1Fully and physically mixing the samples into slurry;
a-3: spreading an aluminum foil on a film coating machine, transferring the stirred sample slurry onto the aluminum foil, uniformly coating the sample slurry, and transferring the sample slurry onto a vacuum drying oven for drying for 12 hours at the drying temperature of 80 ℃;
a-4: the dried material was cut into disks and dried again in vacuum for 6h at 80 ℃.
The step b is further set as follows:
b-1: using CR 2025 button cell shell, Celgard 2400 diaphragm, lithium plate as counter electrode, containing 1 mol. L-1LiPF of6A mixed solvent of an electrolyte and EC (ethylene carbonate)/DEC (diethyl carbonate) (the volume ratio is 1:1) is used as an electrolyte;
b-2: argon-filled glove box (H)2O<0.1ppm,O2<0.1ppm), sequentially placing a positive electrode shell, a positive electrode material sheet, an electrolyte, a diaphragm, the electrolyte, a high-purity lithium sheet, a gasket, an elastic sheet and a negative electrode shell from bottom to top, and compacting the button cell by a tablet press;
b-3: and (5) after standing and activating, carrying out electrochemical performance test.
As mentioned above, the invention provides an electrochemical preparation method of a tellurium-selenium-polyaniline composite material and an energy storage application thereof. The Te is a tellurium selenium-polyaniline composite materialxSeyThe @ PANI can be used as a positive electrode material of a lithium battery and has excellent energy storage performance. The invention discovers that the Te of the tellurium-selenium-polyaniline composite materialxSeyThe @ PANI has better energy storage performance along with higher voltage, provides a brand-new and efficient anode material for energy storage of the lithium battery, and has huge application potential and industrial value in the industrial field.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1 shows Te of Te-Se-polyaniline composite material prepared in example 1 of the present inventionxSeyLow power Scanning Electron Micrograph (SEM) of @ PANI;
FIG. 2 shows Te of Te-Se-polyaniline composite material prepared in example 1 of the present inventionxSeyA Transmission Electron Micrograph (TEM) of @ PANI (FIG. 2a), an elemental energy spectrum peak map (EDX spectrum) (FIG. 2b), and an elemental distribution map (EDS-STEM elemental mapping) (FIG. 2 c);
FIG. 3 shows Te of Te-Se-polyaniline composite material prepared in example 1 of the present inventionxSey@ PANI and Te prepared under different voltagesxSeyX-ray diffraction Pattern contrast plot (XRD) for @ PANI;
FIG. 4 shows Te of Te-Se-polyaniline composite material prepared in example 1 of the present inventionxSeyX-ray photoelectron spectroscopy (XPS) for @ PANI;
FIG. 5 shows Te of Te-Se-polyaniline composite material prepared in example 1 of the present inventionxSey@ PANI and Te prepared under different voltagesxSeyThermogravimetric analysis contrast (TG) (FIG. 5a), differential scanning calorimetry contrast (DSC) (FIG. 5b), Raman (Raman) (5c), Infrared (IR) spectra (FIG. 5d) for @ PANI;
FIG. 6 shows Te of Te-Se-polyaniline composite material prepared in example 1 of the present inventionxSey@ PANI and Te prepared under different voltagesxSeyComparative electrochemical Performance plot of @ PANI: rate capability (FIG. 6a), cycling stability (FIG. 6b), and Te from example 1xSey@ PANI at 0.5A cm-3Cycling stability and coulombic efficiency after 2000 cycles of lower cycling (FIG. 6c), Te from example 1xSey@ PANI at 2.0A cm-3Cycling stability performance and coulombic efficiency after 500 cycles of lower cycling (fig. 6 d);
FIG. 7 shows Te of Te-Se-polyaniline composite material prepared in example 1 of the present inventionxSeyElectrochemical Performance plot of @ PANI: charge-discharge curve graph (FIG. 7a) at different multiplying power and 0.5mV · s-1Cyclic voltammogram at sweep rate (FIG. 7b), FIG. 7c is the tellurium selenium-polyaniline prepared in example 1 of the present inventionComposite material TexSey@ PANI and Te prepared under different voltagesxSeyComparative AC impedance test plot for @ PANI.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1
S1: tellurium powder and selenium powder are used as raw materials, and a tellurium-selenium alloy rod is synthesized by high-temperature annealing, and the method comprises the following steps:
s1-1: grinding tellurium powder and selenium powder in a mass ratio of 10:1 for 30min to enable the particles to be fine and uniformly mixed, placing the mixture on a quartz tube, transferring the quartz tube into a vacuum packaging instrument, and slowly vacuumizing for 30 min;
s1-2: burning the quartz tube at high temperature by using a hydrogen flame spray gun, and carrying out vacuum packaging on the sample;
s1-3: carrying out high-temperature annealing in a tube furnace for 12h after vacuum packaging, wherein the annealing temperature is set to be 500 ℃, and the heating rate is 5 ℃ per minute-1Introducing nitrogen for protection;
s1-4: after high-temperature annealing, vacuum drying the sample for 12h, and setting the drying temperature to be 60 ℃ to obtain a tellurium-selenium alloy rod;
s2: preparing aniline alkali liquor as electrolyte, and the specific steps are as follows:
s2-1: dissolving 1.0g of sodium hydroxide flaky particles in 25ml of deionized water, and fully stirring for 30min until all the sodium hydroxide flaky particles are dissolved;
s2-2: 1.14mL of aniline solution is extracted and added into the prepared sodium hydroxide solution, and the mixture is fully stirred for 1 hour until the aniline solution is completely dissolved;
s2-3: the solution was transferred to a volumetric flask (50mL) and the volume was constant to obtain a basic aniline solution. The solution composition is: 0.5mol L-1NaOH-0.25mol L-1A mixed solution of aniline.
S3: the tellurium-selenium-polyaniline composite material is prepared by taking a tellurium-selenium alloy rod as a working electrode, a calomel electrode as a reference electrode and a Pt wire as a counter electrode in an aniline alkaline solution electrolyte through a constant voltage electrochemical method, and the method comprises the following specific steps:
s3-1: taking a tellurium-selenium alloy rod as a working electrode, a calomel electrode as a reference electrode and a Pt wire as a counter electrode, setting the voltage to be 1.4V in an aniline alkaline solution electrolyte under an i-t mode, reacting for 24h, and separating out and depositing a material on the Pt wire of the counter electrode;
s3-2: washing the obtained material with deionized water for multiple times, centrifuging, and vacuum drying at 60 deg.C for 12h to obtain Te of tellurium-selenium-polyaniline composite materialxSey@ PANI, noted M1;
s4: the preparation method of the tellurium selenium-polyaniline positive electrode material sheet of the button cell comprises the following steps:
s4-1: taking positive electrode material TexSey@ PANI 100mg, conductive agent acetylene black 21.4mg, binder PVDF (polyvinylidene fluoride) 21.4mg, fully grinding until the particles are uniform, and transferring to a weighing bottle;
s4-2: dropping 600-1000 μ L NMP (N-methyl pyrrolidone) into the mixture by using a liquid transfer gun, stirring for 24h at normal temperature and 600r min-1Fully and physically mixing the samples into slurry;
s4-3: spreading an aluminum foil on a film coating machine, transferring the stirred sample slurry onto the aluminum foil, uniformly coating the sample slurry, and transferring the sample slurry onto a vacuum drying oven for drying for 12 hours at the drying temperature of 80 ℃;
s4-4: the dried material was cut into disks and dried again in vacuum for 6h at 80 ℃.
S5: assembling the button cell with the tellurium-selenium-polyaniline composite material as the anode material and Li as the cathode material, and performing energy storage application, wherein the specific steps are as follows:
s5-1: using CR 2025 button cell shell, Celgard 2400 diaphragm, lithium plate as counter electrode, containing 1 mol. L-1LiPF of6A mixed solvent of an electrolyte and EC (ethylene carbonate)/DEC (diethyl carbonate) (the volume ratio is 1:1) is used as an electrolyte;
s5-2: argon-filled glove box (H)2O<0.1ppm,O2<0.1ppm), sequentially placing a positive electrode shell, a positive electrode material sheet, a lithium sulfur electrolyte, a diaphragm, the lithium sulfur electrolyte, a high-purity lithium sheet, a gasket, an elastic sheet and a negative electrode shell from bottom to top, and pressing the button by using a tablet pressCompacting the battery;
s5-3: and (5) after standing and activating, carrying out electrochemical performance test.
EXAMPLES 2-3 examination of the resulting Voltage
Except that the tellurium-selenium-polyaniline composite material M1 was prepared at 1.4V in S3, the tellurium-selenium-polyaniline composite materials were prepared at different voltages shown in Table 1 below. The other operations were the same as in example 1, thus carrying out examples 2 and 3, and the different composites obtained were named as shown in table 1 below.
TABLE 1 composite materials of different material compositions
Microscopic characterization
Te of the Te Se-polyaniline composite material obtained in example 1xSey@ PANI microscopic characterization was performed by a number of different means, with the following results:
1. as can be seen from the low-power Scanning Electron Microscope (SEM) of FIG. 1, the Te of the Te-Se-polyaniline composite materialxSeyThe @ PANI is a rod-shaped structure, the surface of the @ PANI is provided with a layered wrapping object, and the length of the rod is 400-600 nm.
2. As can be seen from the TEM image of the transmission electron microscope of fig. 2a, the observed morphology of the sample is consistent with the profile of the morphology of the sample observed on the SEM, and the presence of the layered wrap on the rod-like structure is consistent with the SEM results.
FIG. 2b is TexSeyThe EDX characterization of the @ PANI component can find the composition of Te, Se, C, N, O and other elements in the material.
FIG. 2C is a distribution diagram of elements of the obtained material, and it can be seen from the figure that Te, Se, C, N, O and other elements are uniformly distributed on the rod-like structure, and C, N elements are distributed on the outer ring of the rod-like structure, which proves that the material is Te wrapped by polyaniline polymerxSeyA material.
3. As seen from the X-ray diffraction pattern (XRD) of FIG. 3, two peaks appear corresponding to the Se (101) and Te (011) crystal planes, respectively; within the range of 24-30 degrees, three characteristic peaks of a comparative simple substance Te，TexSeyThe @ PANI only has one characteristic peak, and the reason may be that Se atoms are doped into Te crystal lattices to generate defects, so that the crystal form of part of crystal faces of the crystal faces is deteriorated. Second, the Te (011) crystal plane peak is shifted, indicating a change in its lattice parameters, probably due to the incorporation of Se atoms into the Te lattice. In addition, in the product synthesized at 1.4V, M1, two new XRD peaks appeared around 20 deg., with the possibility of forming TexSeyPhase, thereby creating new crystal planes.
4. As can be seen from the X-ray photoelectron spectroscopy (XPS) chart of FIG. 4, the elements Te, Se, N, C, O are present in TexSey@ PANI (M1); in fig. 4b, the electron binding energies of C ═ O bond, C — N/C ═ N bond, and C — C/C — H bond of the carbon skeleton of the benzene ring can be obtained, which further proves that the polymer coated on the surface is polyaniline; FIG. 4c shows Te is Te in the composite material6+、Te4+The form exists; in FIG. 4d, the Se 3d bond is mainly a Te-Se 3d bond5/2Bonds, indicating that part of the Se is also oxidized to Se at the working electrode6+. From the analysis in FIG. 4, Te was obtained by the electrochemical methodxSey@ PANI where Te and Se are both in positive valence state, then it may be TexSeyOzExist in the form of (1).
5. The product TG of fig. 5a is characterized by the fact that it is seen that the active species is as high as 88% at voltages of 0.8V (M3) and 1.1V (M2), and 67% at 1.4V, indicating a high active species loading. Secondly, with the increase of voltage, the wrapping amount of polyaniline macromolecules is increased; FIG. 5b is TexSeyDSC characterization of the @ PANI component shows two obvious endothermic peaks at 251 ℃ and 440 ℃ respectively, and proves TexSeyThe @ PANI component has phase change at the two temperatures, which respectively correspond to the phase change temperatures of Se and Te, so that the material can be proved to contain Te and Se elements; as can be seen from FIG. 5c, 100--1Two Raman peaks appear, which respectively correspond to the A1 peak and the E peak of Te, and are 238cm-1And 600cm-1、700cm-1The three peaks are Raman peaks of Se, and the product is proved to contain Te and Se elements; IR characterization from FIG. 5dN-H stretching vibration, C-H stretching vibration, and C ═ C bond stretching vibration can be seen, corresponding to the benzene ring skeleton. Therefore, the product can be judged to be TexSey@PANI。
Preparation method of battery electrode M1
A. Taking TexSeyThe @ PANI composite material M1, the acetylene black and the PVDF are fully ground in an agate mortar according to the proportion of (7:1.5:1.5) until the samples are uniformly mixed. After the sample was transferred to a weighing bottle after grinding, N-methylpyrrolidone (NMP) was added dropwise as a solvent using a pipette. Stirring for 6-12h at normal temperature until uniform, and fully and physically mixing the samples into slurry.
B. Spreading the aluminum foil on a film coating machine, transferring the stirred sample slurry to the aluminum foil to be uniformly coated, and then transferring the whole aluminum foil material coated with the slurry to a vacuum drying oven to be dried for 6-12h at the drying temperature of 60-120 ℃. Then taking out the material slice, cutting the material slice into round slice materials with certain sizes, and then drying the round slice materials in vacuum for 6 to 12 hours at the temperature of between 60 and 120 ℃. Then taking out, weighing, drying and storing.
C. A CR 2025 button battery case, a Celgard 2400 diaphragm and a lithium sheet are selected as counter electrodes. The electrolyte solution contains 1mol L-1LiPF of6A mixed solvent of an electrolyte and Ethylene Carbonate (EC)/diethyl carbonate (DEC) (volume ratio of 1: 1). In a glove box filled with argon (H2O)<0.1ppm,O2<0.1ppm), sequentially placing a positive electrode shell, a positive electrode material sheet, electrolyte, a diaphragm, the electrolyte, a high-purity lithium sheet, a gasket, an elastic sheet and a negative electrode shell from bottom to top, and compacting the button cell by a tablet press. And (5) after standing and activating, carrying out electrochemical performance test.
Preparation method of lithium battery electrode M2-M3
The above-described "method for producing a lithium battery electrode M1" was carried out by replacing the composite material M1 with M2 and M3, respectively, and the other operations were not changed, so that the above-described production methods were repeated, and battery electrodes using M2 and M3 were obtained in this order and were named as an M2 electrode material and an M3 electrode material, respectively.
Electrochemical performance test
1. FIG. 6a is a graph showing the rate capability test of M1 electrode material, M2 electrode material and M3 electrode material
As can be seen from the figure, the distance is 0.1-5.0A cm-3The multiplying power is respectively circulated for 10 circles, the multiplying power performance of the material is increased along with the increase of voltage, and particularly when the voltage is 1.4V, the multiplying power performance is obviously higher than 1.1V and 0.8V. The reason may be that the conductive polymer polyaniline is wrapped, so that on one hand, the conductivity of the material is improved, and on the other hand, Te is effectively hinderedxSeyThe @ PANI component expands in volume during charging and discharging. In addition, the Te lattice parameter is increased due to the formation of Te-Se bond, so that Li+Can enter into Te crystal lattice in the discharge process, and effectively inhibit the volume expansion of the material in the charge-discharge process.
2. FIG. 6b is a graph showing the cycle performance test of M1 electrode material, M2 electrode material and M3 electrode material
Te obtained at a voltage of 1.4VxSeyThe circulation stability of the @ PANI component is obviously higher than Te obtained under the voltage of 1.1V and 0.8VxSey@ PANI component. At 0.5A cm-3After 1000 cycles of lower circulation, the capacity is kept at 372mA h cm-3. And its capacity instead shows an upward trend during the cycle. At 2.0A cm-3After 500 cycles of lower circulation, the capacity is kept at 99.8mA h cm-3Thus, Li-Te was foundxSeyThe battery exhibits high rate performance. On the other hand, the battery capacity is still relatively fast to decay, and it may be that the material still contains simple substance tellurium, and the volume expansion occurs during the charging and discharging process, so that the battery capacity is fast to decay.
3. FIG. 6c is a test chart of the cycle performance of M1 electrode material
As can be seen from the graph, Te obtained at a voltage of 1.4VxSeyThe circulation stability of the @ PANI component is obviously higher than Te obtained under the voltage of 1.1V and 0.8VxSey@ PANI component. At 0.5A cm-3After 1000 cycles of lower circulation, the capacity is kept at 372mA h cm-3. And its capacity instead shows an upward trend during the cycle.
4. FIG. 6d is a test chart of the cycle performance of M1 electrode material
As can be seen from the figure, at 2.0A cm-3After 500 cycles of lower circulation, the capacity is kept at 99.8mA h cm-3Thus, Li-Te was foundxSeyThe battery exhibits high rate performance. On the other hand, the battery capacity is still relatively fast to decay, and it may be that the material still contains simple substance tellurium, and the volume expansion occurs during the charging and discharging process, so that the battery capacity is fast to decay.
5. FIG. 7a is a graph showing the charge/discharge performance test of M1 electrode material
TexSey@ PANI component at 0.1Acm-3The discharge of the lower first circle can reach 586mAh cm-3。
6. FIG. 7b is a cyclic voltammetry test chart of M1 electrode material
To evaluate TexSeyThe electrochemical performance of the @ PANI component is 1-2mg cm of active substance loading capacity-2And (4) coating, slicing and assembling the material into the button cell. For Te obtained at 1.4VxSeyThe @ PANI component was subjected to cyclic voltammetry, scanning at a rate of 0.5mV s over a voltage window of 1-3V for five cycles-1. As shown in FIGS. 4-7b, the two cathodic peaks in the first turn, representing Li, appear at 1.75V and 1.50V2Te2/Li2Te and Li2And forming Se. The conventional Li-Se cell shows only one cathode peak at 1.5V, and the conventional Li-Te cell shows two cathode peaks at 1.56V and 1.68V. Second, 2.2V appears at the anode peak, slightly higher than 1.82V for a typical lithium battery. Second, it can be seen from 4-7a that the discharge curve exhibits two discharge plateaus, corresponding to two cathodic peaks in the CV.
7. FIG. 7c is a cyclic voltammetry test chart of M1 electrode material, M2 electrode material and M3 electrode material
To compare the voltage pairs TexSeyElectrochemical Effect of the @ PANI component three Te were obtained at 0.8V, 1.1V, 1.4VxSeyThe @ PANI component was subjected to AC impedance analysis, and as can be seen from FIGS. 4-7b, the impedance of the product decreased in sequence as the voltage increased. From this, it is seen that the amount of the surface conductive polymer wrapped increases due to the increase of the voltage, therebyIncreasing the conductivity of the material.
Thus proving that the Te of the tellurium-selenium-polyaniline composite material of the inventionxSeyThe @ PANI has excellent lithium storage performance and can be used for energy storage.
In summary, it can be seen from all the above embodiments that the preparation method of the invention obtains the tellurium-selenium-polyaniline composite material Te with unique morphology through the synergistic combination and coordination of specific process steps, process parameters and the likexSey@ PANI, and it has good energy storage properties.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (10)
1. An electrochemical preparation method of a tellurium-selenium-polyaniline composite material is characterized by comprising the following steps:
s1: tellurium powder and selenium powder are used as raw materials, are ground, mixed uniformly and then are packaged in vacuum, and a tellurium-selenium alloy rod is synthesized through high-temperature annealing;
s2: dissolving aniline solution in alkali liquor to prepare alkaline electrolyte containing aniline solution;
s3: and (3) taking the tellurium-selenium alloy rod prepared in the step (S1) as a working electrode, taking a calomel electrode as a reference electrode and taking a Pt wire as a counter electrode, and preparing the tellurium-selenium-polyaniline composite material in alkaline electrolyte containing aniline solution prepared in the step (S2) by a constant voltage electrochemical method.
2. The electrochemical preparation method of the tellurium-selenium-polyaniline composite material as claimed in claim 1, wherein: in step S1, the mixing mass ratio of the tellurium powder to the selenium powder is 1-40: 1.
3. The electrochemical preparation method of the tellurium-selenium-polyaniline composite material as claimed in claim 1, wherein: in step S1, the temperature of the high temperature annealing treatment is 400-600 ℃, and the time of the annealing treatment is 2-48 hours.
4. The electrochemical preparation method of the tellurium-selenium-polyaniline composite material as claimed in claim 1, wherein: in step S1, the temperature rise rate in the high-temperature annealing treatment is 1-9 ℃ for min-1。
5. The electrochemical preparation method of the tellurium-selenium-polyaniline composite material as claimed in claim 1, wherein: in step S2, the alkali solution is one of an aqueous solution of sodium hydroxide, an aqueous solution of sodium carbonate, an aqueous solution of sodium bicarbonate, an aqueous solution of sodium acetate, and ammonia water.
6. The electrochemical preparation method of the tellurium-selenium-polyaniline composite material as claimed in claim 1, wherein: in step S2, the concentration of the alkali liquor is 0-3mol L-1。
7. The electrochemical preparation method of the tellurium-selenium-polyaniline composite material as claimed in claim 1, wherein: in step S2, the aniline concentration is 0-0.4mol L-1。
8. The electrochemical preparation method of the tellurium-selenium-polyaniline composite material as claimed in claim 1, wherein: in step S3, the voltage of the constant voltage electrochemical method may be set to 0.1-3.0V, and the reaction time is 1-96 h.
9. The tellurium-selenium-polyaniline composite material prepared by the electrochemical preparation method as claimed in claim 1.
10. An energy storage application of the tellurium-selenium-polyaniline composite material as claimed in claim 9, wherein: the tellurium selenium-polyaniline composite material is used as a positive electrode material of a battery.
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