CN115050936B - Bi 0.67 Sb 1.33 S 3 PEDOT@LA composite material and preparation and application thereof - Google Patents
Bi 0.67 Sb 1.33 S 3 PEDOT@LA composite material and preparation and application thereof Download PDFInfo
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- ethylenedioxythiophene
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- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims description 13
- 229960002663 thioctic acid Drugs 0.000 claims abstract description 59
- AGBQKNBQESQNJD-UHFFFAOYSA-M lipoate Chemical compound [O-]C(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-M 0.000 claims abstract description 32
- 235000019136 lipoic acid Nutrition 0.000 claims abstract description 32
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- JWVUFVZEYBYBAL-UHFFFAOYSA-N [Bi]=S.[Sb] Chemical compound [Bi]=S.[Sb] JWVUFVZEYBYBAL-UHFFFAOYSA-N 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 239000008367 deionised water Substances 0.000 claims description 49
- 229910021641 deionized water Inorganic materials 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 45
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 41
- 239000008188 pellet Substances 0.000 claims description 37
- 239000000047 product Substances 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 31
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 25
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 230000007935 neutral effect Effects 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 15
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 15
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 14
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 19
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052700 potassium Inorganic materials 0.000 abstract description 7
- 239000011591 potassium Substances 0.000 abstract description 7
- 238000009830 intercalation Methods 0.000 abstract description 6
- 230000002687 intercalation Effects 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 5
- 230000001351 cycling effect Effects 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 5
- 238000004146 energy storage Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 13
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 12
- 239000007772 electrode material Substances 0.000 description 12
- 239000010405 anode material Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 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
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal sulfides Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a Bi 0.67 Sb 1.33 S 3 The PEDOT@LA composite material is characterized in that the composite material has a structure that a hollow poly 3, 4-ethylenedioxythiophene network is coated with a layer of organic lipoic acid and is loaded with antimony sulfide bismuth nano particles. Compared with the prior art, the Bi prepared by the invention 0.67 Sb 1.33 S 3 The hollow PEDOT network of the/PEDOT@LA composite material can provide faster mass transfer and charge transfer paths and relieve Bi 0.67 Sb 1.33 S 3 The volume change in the potassium intercalation process improves the cycling stability of the electrode; the lipoic acid is connected with the PEDOT through hydrogen bonds to form a dynamic self-adaptive energy storage interface, disulfide bonds in the lipoic acid can be polymerized in situ in the battery charging process, and the structural stability and K of the material are improved + Storage capacity.
Description
Technical Field
The invention relates to the field of battery materials, in particular to a composite material (Bi) taking poly-3, 4-ethylenedioxythiophene as a conductive matrix to load antimony sulfide bismuth and lipoic acid 0.67 Sb 1.33 S 3 PEDOT@LA), a preparation method thereof and application thereof as a cathode material of a potassium ion battery.
Background
With the wide application of lithium ion batteries in portable devices such as mobile phones and notebook computers, the demand for high-performance and safe lithium ion batteries is increasing. However, lithium resources are limited in reserves, maldistributed, and limit the development of applications in new electrical energy storage technologies. Recently, potassium has been found to be a resource rich, low cost, fast K in traditional carbonate electrolytes + Transmission kinetics, and higher energy density than sodium ion batteries, make potassium ion batteries very attractive. However, potassium ions have a large radius, which makes the volume of the electrode material vary greatly during charge and discharge, resulting in slow chemical kinetics and poor cycling stability.
The negative electrode material is required to have high capacity and long cycle stability to promote potassium as an important constituent of a batteryFurther developments in ion batteries. Currently, reported anode materials mainly include intercalation species, organic compounds, alloys, and transformation species, depending on the reaction mechanism. The intercalation type anode mainly comprises a carbon material and a titanium-based material, which have fixed gaps or interlayer spacing to promote K + Transmission without significant structural changes, while these materials exhibit high cycling stability, the limited capacity makes it difficult to achieve high energy densities. Organic materials, while having low cost, environmental friendliness, and flexible structure, have disadvantages such as being readily soluble in electrolytes, poor electronic conductivity, and relatively low energy density. Transformed anode materials, such as transition metal sulfides, can provide high specific capacities, but these materials typically have large volume changes and relatively high operating voltages, poor cycling stability and low energy density in full cell configurations. The alloy material has relatively high theoretical capacity and low oxidation-reduction potential, ensures high energy density and battery safety, but the practical application is still limited by the problems of long cycle life, low coulombic efficiency and the like. Therefore, each material has respective advantages and disadvantages, two or more types of materials are combined, the advantages and disadvantages are compensated, and the development of an organic and inorganic composite material has important significance for realizing a high-performance potassium ion battery.
Disclosure of Invention
Bi 0.67 Sb 1.33 S 3 As a bimetallic sulfide, the combination of high theoretical capacity of Sb (660 mAh/g) and excellent rate capability of Bi is a potential anode material of a potassium ion battery, but is still limited by K + Problems of volume expansion during intercalation and deintercalation, bi is also required 0.67 Sb 1.33 S 3 The negative electrode material is further modified to improve the structural stability and the rate capability of the negative electrode material.
In view of the above, an object of the present invention is to provide a composite material (Bi) comprising poly (3, 4-ethylenedioxythiophene) (PEDOT) as a conductive matrix and antimony bismuth sulfide and Lipoic Acid (LA) 0.67 Sb 1.33 S 3 /PEDOT@LA)The composite material is characterized in that a hollow PEDOT network is coated with a layer of organic lipoic acid and loaded with antimony sulfide bismuth nanoparticles.
Another object of the present invention is to provide a Bi as described above 0.67 Sb 1.33 S 3 The preparation method of the PEDOT@LA composite material comprises the following steps:
(1) Preparing silica pellets;
(2) Carrying out surface modification on the silica pellets prepared in the step (1);
(3) 3, 4-Ethylenedioxythiophene (EDOT) is polymerized to generate poly 3, 4-ethylenedioxythiophene (PEDOT) and uniformly coated on the surface of the silica pellets, and the silica pellets are completely etched by hydrofluoric acid to obtain hollow PEDOT;
(4) Reacting antimony trichloride, bismuth nitrate pentahydrate, thioacetamide, lipoic acid and the PEDOT through a hydrothermal kettle to obtain a composite material Bi with the PEDOT as a matrix and loaded with antimony bismuth sulfide and lipoic acid 0.67 Sb 1.33 S 3 /PEDOT@LA。
As a preferred embodiment, the Bi 0.67 Sb 1.33 S 3 The preparation method of the PEDOT@LA composite material comprises the following steps:
(1) Mixing water, ethanol and ammonia water, uniformly dispersing by ultrasonic waves, adding tetraethoxysilane, stirring for 3-4 hours at 30-40 ℃, centrifuging the product, washing the obtained precipitate with deionized water and ethanol for 3-5 times, and drying the washed product to obtain silica pellets;
(2) Taking the silica pellets obtained in the step (1), dispersing in acetic acid by ultrasonic, adding hydrogen peroxide, dispersing uniformly by ultrasonic, adding 3-mercaptopropyl trimethoxysilane, stirring at 80 ℃ for 2-2.5 h, washing the obtained product with deionized water to be neutral, and centrifuging to obtain modified silica pellets;
(3) Dissolving the modified silica pellets obtained in the step (2) in deionized water to form a mixed solution, transferring the mixed solution into the deionized water, adding concentrated hydrochloric acid, performing ultrasonic dispersion uniformly, adding EDOT, and performing ultrasonic dispersion uniformly; dissolving ammonium persulfate in deionized water, slowly dropwise adding the ammonium persulfate solution into the mixed solution containing EDOT, stirring at 30 ℃ for 12-13 h, washing the obtained product with deionized water to be neutral, centrifuging to obtain precipitate, dispersing the precipitate into the deionized water, adding hydrofluoric acid, stirring for 3h, washing to be neutral, and centrifuging to obtain hollow PEDOT;
(4) Dissolving the hollow PEDOT obtained in the step (3) in ethylene glycol, adding thioacetamide, and stirring to dissolve the thioacetamide; dissolving antimony trichloride and bismuth nitrate pentahydrate in ethylene glycol, and stirring to form a uniform mixed solution; mixing the two solutions together, stirring for 0.5-1 h, adding lipoic acid, continuously stirring for 1-2 h, then transferring into a hydrothermal kettle, and reacting at 60 ℃ for 22-24 h; washing the obtained product with deionized water and ethanol for 3-5 times, and centrifuging to obtain Bi 0.67 Sb 1.33 S 3 PEDOT@LA composite material.
Preferably, in the step (1), the volume ratio of the water to the ethanol to the ammonia water is (4-6): 20-23): 1, the volume ratio of the tetraethoxysilane to the ammonia water is 1 (1.1-1.3), and the centrifugal rotating speed is 7000-9000 r/min.
Preferably, in the step (2), the mass-volume ratio of the silica pellets to the 3-mercaptopropyl trimethoxysilane is (1-1.2) g/10 mL.
Preferably, in the step (3), the mass ratio of the 3, 4-ethylenedioxythiophene to the concentrated hydrochloric acid to the ammonium persulfate is 1 (2.4-2.6): (1.8-1.9), and the mass volume ratio of the silicon dioxide pellets to the hydrofluoric acid is 0.1g (2.8-3.2) mL.
Preferably, in the step (4), the mass ratio of PEDOT, lipoic acid and thioacetyl is 1 (2.5-3), the molar ratio of antimony trichloride to bismuth nitrate pentahydrate is 4-6, and the molar ratio of antimony trichloride to bismuth nitrate pentahydrate is 1.8-2.2.
It is still another object of the present invention to provide the above Bi 0.67 Sb 1.33 S 3 The application of the PEDOT@LA composite material in a potassium ion battery.
Preferably, the application is to use the Bi 0.67 Sb 1.33 S 3 The PEDOT@LA composite material is used as a negative electrode material of a potassium ion battery.
Compared with the prior art, the invention has the advantages that:
bi prepared by the invention 0.67 Sb 1.33 S 3 The hollow PEDOT network of the/PEDOT@LA composite material can provide faster mass transfer and charge transfer paths and relieve Bi 0.67 Sb 1.33 S 3 The volume change in the potassium intercalation process improves the cycling stability of the electrode; the lipoic acid is connected with the PEDOT through hydrogen bonds to form a dynamic self-adaptive energy storage interface, disulfide bonds in the lipoic acid can be polymerized in situ in the battery charging process, and the structural stability and K of the material are improved + A storage capacity; in addition, bi 0.67 Sb 1.33 S 3 The synthesis temperature of the bimetallic sulfide is only 60 ℃, and compared with the high preparation temperature of the alloy nano-particles, the bimetallic sulfide is easier to mass production.
Drawings
FIG. 1 shows Bi obtained in comparative example 1 0.67 Sb 1.33 S 3 X-ray diffraction analysis pattern of the electrode material.
FIG. 2 is a SiO obtained in example 1 2 Transmission electron microscopy of @ PEDOT.
FIG. 3 shows Bi obtained in example 1 0.67 Sb 1.33 S 3 Transmission electron microscope image of the PEDOT@LA composite electrode material.
FIG. 4 shows Bi obtained in example 1 0.67 Sb 1.33 S 3 And (3) an infrared spectrogram of the PEDOT@LA composite electrode material.
FIG. 5 shows Bi obtained in comparative example 1 0.67 Sb 1.33 S 3 Electrode material and Bi obtained in example 1 0.67 Sb 1.33 S 3 Ratio performance comparison graph of PEDOT@LA composite electrode material.
FIG. 6 shows Bi obtained in comparative example 1 0.67 Sb 1.33 S 3 Electrode material and Bi obtained in example 1 0.67 Sb 1.33 S 3 Cycle performance comparison graph of PEDOT@LA composite electrode material.
Detailed Description
The details and embodiments of the invention will be described below in connection with examples of the invention, but the examples described are only a few examples of the invention, and embodiments of the invention are not limited thereto.
The experimental methods described in the following examples are conventional unless otherwise specified.
Bi provided by the invention 0.67 Sb 1.33 S 3 The preparation method of the PEDOT@LA composite material comprises the following steps:
(1) Mixing water, ethanol and ammonia water, and then uniformly dispersing by ultrasonic, wherein the volume ratio of the water to the ethanol to the ammonia water is (4-6): 20-23): 1, then adding tetraethoxysilane, wherein the volume ratio of the added tetraethoxysilane to the ammonia water is 1 (1.1-1.3), stirring for 3-4 hours at 30-40 ℃, centrifuging the product, the centrifuging speed is 7000-9000 r/min, washing the obtained precipitate with deionized water and ethanol for 3-5 times, and drying the washed product at 60 ℃ to obtain silica pellets;
(2) Taking 0.045-0.050 g of the silica pellets obtained in the step (1), dispersing in 14-16 mL of acetic acid by ultrasonic, adding 1.9-2.2 mL of hydrogen peroxide, dispersing uniformly by ultrasonic, adding 0.4-0.6 mL of 3-mercaptopropyl trimethoxysilane, stirring at 80 ℃ for 2-2.5 h, washing the obtained product with deionized water to be neutral, and centrifuging to obtain modified silica pellets;
(3) Dissolving the modified silica pellets obtained in the step (2) in 5-10 g of deionized water to form a mixed solution, transferring the mixed solution into 50-60 g of deionized water, adding 0.24-0.26 g of concentrated hydrochloric acid, uniformly dispersing by ultrasonic, adding 0.08-0.15 g of EDOT, and uniformly dispersing by ultrasonic; weighing 0.182-0.186 g of ammonium persulfate to be dissolved in 5-10 g of deionized water, slowly dripping the ammonium persulfate solution into the mixed solution containing EDOT, and stirring for 12-13 h at 30 ℃; washing the obtained product to be neutral by using deionized water, centrifuging to obtain a precipitate, dispersing the precipitate into 20-30 mL of deionized water, adding 1.5-1.6 mL of hydrofluoric acid, stirring for 3h, washing to be neutral, and centrifuging to obtain hollow PEDOT;
(4) Dissolving the hollow PEDOT obtained in the step (3) in 20-30 mL of ethylene glycol, adding 0.084-0.086 g of thioacetamide, and stirring to dissolve the thioacetamide;0.08-0.14 g of antimony trichloride and 0.09-0.15 g of bismuth nitrate pentahydrate are weighed, dissolved in 20-30 mL of glycol and stirred to form a uniform mixed solution; mixing the two solutions together, stirring for 0.5-1 h, adding lipoic acid, continuously stirring for 1-2 h, then transferring into a hydrothermal kettle, and reacting at 60 ℃ for 22-24 h; washing the obtained product with deionized water and ethanol for 3-5 times, centrifuging to obtain precipitate, dissolving the precipitate in 20-30 mL of ethanol, adding 0.02-0.03 g of lipoic acid, stirring for 4-6 h, centrifuging to obtain Bi 0.67 Sb 1.33 S 3 PEDOT@LA composite material.
Example 1
(1) Mixing 10mL of water, 46mL of ethanol and 2mL of ammonia water, uniformly dispersing by ultrasonic, adding 2.2mL of tetraethoxysilane, stirring for 4 hours at 30 ℃, centrifuging the product at 9000r/min, washing the obtained precipitate with deionized water and ethanol for 3 times, and drying the washed product at 60 ℃ to obtain silica pellets;
(2) Taking 0.048g of the silica pellets obtained in the step (1), dispersing in 14mL of acetic acid by ultrasonic, adding 2mL of hydrogen peroxide, dispersing uniformly by ultrasonic, adding 0.4mL of 3-mercaptopropyl trimethoxysilane, stirring at 80 ℃ for 2 hours, washing the obtained product with deionized water to be neutral, and centrifuging to obtain modified silica pellets;
(3) Dissolving the modified silica pellets obtained in the step (2) in 6g of deionized water to form a mixed solution, transferring the mixed solution into 54g of deionized water, adding 0.25g of concentrated hydrochloric acid, uniformly dispersing by ultrasonic, adding 0.1g of 3, 4-ethylenedioxythiophene, and uniformly dispersing by ultrasonic; 0.183g of ammonium persulfate is weighed and dissolved in 5g of deionized water, and the ammonium persulfate solution is slowly dripped into the mixed solution containing 3, 4-ethylenedioxythiophene and stirred for 12 hours at 30 ℃; washing the obtained product to be neutral by using deionized water, centrifuging to obtain a precipitate, dispersing the precipitate into 20mL of deionized water, adding 1.5mL of hydrofluoric acid, stirring for 3 hours, washing to be neutral, and centrifuging to obtain hollow PEDOT;
(4) Dissolving the hollow PEDOT obtained in the step (3) in 20mL of ethylene glycol, adding 0.085g of thioacetamide, and stirring to dissolve the thioacetamide; 0.086g of antimony trichloride and 0.09 g of1g of bismuth nitrate pentahydrate, dissolving the bismuth nitrate pentahydrate and the bismuth nitrate pentahydrate in 20mL of ethylene glycol, and stirring to form a uniform mixed solution; mixing the two solutions together, stirring for 1h, adding 0.03g of lipoic acid, continuously stirring for 2h, then transferring into a hydrothermal kettle, and reacting at 60 ℃ for 24h; washing the obtained product with deionized water and ethanol for 3 times, and centrifuging to obtain Bi 0.67 Sb 1.33 S 3 PEDOT@LA composite material.
As can be seen from the transmission electron microscope of FIG. 2, siO 2 The diameter of the small ball is 100-150 nm, and the surface of the small ball is uniformly coated with a layer of PEDOT; as can be seen from the transmission electron microscope of FIG. 3, bi 0.67 Sb 1.33 S 3 The diameter of the nano particles is small, the nano particles are uniformly deposited on the PEDOT conductive network through electrostatic action, and LA is coated on the surface of the PEDOT through hydrogen bond action; FIG. 4 shows that Bi can be seen from the characteristic peaks of the infrared spectrogram of the composite material 0.67 Sb 1.33 S 3 PEDOT and LA were successfully composited together.
The Bi obtained is then reacted with 0.67 Sb 1.33 S 3 The PEDOT@LA composite electrode material, conductive carbon black (Super P) and a binder (polyvinylidene fluoride, PVDF) are mixed and stirred uniformly according to the mass ratio of 7:2:1, 1-methyl-2-pyrrolidone solvent (NMP) is added dropwise to prepare uniform slurry, the uniform slurry is coated on copper foil, the copper foil is put into a baking oven at 90 ℃ and dried for 12 hours, and a working electrode plate is obtained after cutting. Then, in a glove box filled with argon, a potassium ion battery is assembled by taking a potassium sheet as a counter electrode and 3M KFSI dissolved in DME as an electrolyte.
Comparative example 1
0.086g of antimony trichloride and 0.091g of bismuth nitrate pentahydrate are weighed, dissolved in 20mL of ethylene glycol, stirred to form a uniform mixed solution, and 0.085g of thioacetamide is weighed and dissolved in 20mL of ethylene glycol, and fully stirred to be dissolved; mixing the two solutions together, stirring for 2 hours, then transferring into a hydrothermal kettle, and reacting at 60 ℃ for 24 hours; washing the obtained product with deionized water and ethanol for 3 times, and centrifuging to obtain Bi 0.67 Sb 1.33 S 3 A material.
The Bi obtained is then reacted with 0.67 Sb 1.33 S 3 Electrode material assembled into potassium ionThe conditions of the subcell were the same as in example 1.
As can be seen from the X-ray diffraction analysis chart of FIG. 1, the diffraction peaks and Bi of the sample 2 S 3 、Sb 2 S 3 Diffraction card peaks correspond to each other, and no other impurity crystal faces exist, which proves that Bi 0.67 Sb 1.33 S 3 Is a successful synthesis of (a).
Performance testing
Example 1 and comparative example 1 were compared, and the comparison results are shown in detail in fig. 5 and 6. FIG. 5 is Bi 0.67 Sb 1.33 S 3 And Bi (Bi) 0.67 Sb 1.33 S 3 Ratio performance comparison graph of PEDOT@LA as anode material of potassium ion battery under different current densities, and FIG. 6 is Bi 0.67 Sb 1.33 S 3 And Bi (Bi) 0.67 Sb 1.33 S 3 Cycle performance chart comparison chart of PEDOT@LA as potassium ion battery anode material at 0.5A/g, from which Bi can be seen 0.67 Sb 1.33 S 3 PEDOT@LA composite material to pure Bi 0.67 Sb 1.33 S 3 The material has small capacity attenuation degree and more excellent multiplying power performance and cycle performance, and the addition of PEDOT and LA can improve the mechanical performance of the material, effectively inhibit the volume expansion problem of the material and improve the multiplying power and cycle performance of the material.
Bi 0.67 Sb 1.33 S 3 The structure of the PEDOT@LA is Bi 0.67 Sb 1.33 S 3 The nanoparticles are electrostatically adsorbed on the hollow PEDOT, and Lipoic Acid (LA) is linked to the PEDOT by hydrogen bonding. The composite material has the following advantages: first, bi 0.67 Sb 1.33 S 3 Combines high theoretical capacity (660 mAh/g) of Sb and excellent multiplying power performance of Bi, and S is introduced 2- Can be combined with K + Reversible reactions occur to provide additional capacity, particulate Bi 0.67 Sb 1.33 S 3 The nano material can relieve stress change, and the larger specific surface area can promote K + Is transmitted by the base station; second, PEDOT causes pi electron energy state change of the polymer chain due to proton acid doping, thereby generating strong electric conduction capability, and the positive charge carried by PEDOT itself can be realizedAdsorption of polysulfide, inhibition of shuttle effect, and increased contact area of electrolyte with active material due to hollow PEDOT, facilitating K + The prepared whole PEDOT conductive network can improve the electronic conductivity, has good mechanical elasticity and can relieve Bi 0.67 Sb 1.33 S 3 Volume change of nano particles in potassium removal and intercalation process, and K is improved + Is a diffusion rate of (a); third, the hydrogen bond formed between the carboxyl group and PEDOT in the lipoic acid can inhibit the lipoic acid from being dissolved in the electrolyte, and can induce the charge transfer and the formation of cationic free radicals, disulfide bond in the lipoic acid can be polymerized in situ during the charging process of the battery, and the stability of the electrode interface is enhanced, so Bi 0.67 Sb 1.33 S 3 PEDOT@LA has excellent electrochemical properties as a negative electrode material of a potassium ion battery.
Example 2
(1) Mixing 10mL of water, 46mL of ethanol and 2mL of ammonia water, uniformly dispersing by ultrasonic, adding 2.2mL of tetraethoxysilane, stirring for 4 hours at 30 ℃, centrifuging the product at 9000r/min, washing the obtained precipitate with deionized water and ethanol for 3 times, and drying the washed product at 60 ℃ to obtain silica pellets;
(2) Taking 0.048g of the silica pellets obtained in the step (1), dispersing in 14mL of acetic acid by ultrasonic, adding 2mL of hydrogen peroxide, dispersing uniformly by ultrasonic, adding 0.4mL of 3-mercaptopropyl trimethoxysilane, stirring at 80 ℃ for 2 hours, washing the obtained product with deionized water to be neutral, and centrifuging to obtain modified silica pellets;
(3) Dissolving the modified silica pellets obtained in the step (2) in 6g of deionized water to form a mixed solution, transferring the mixed solution into 54g of deionized water, adding 0.25g of concentrated hydrochloric acid, uniformly dispersing by ultrasonic, adding 0.1g of 3, 4-ethylenedioxythiophene, and uniformly dispersing by ultrasonic; 0.183g of ammonium persulfate is weighed and dissolved in 5g of deionized water, and the ammonium persulfate solution is slowly dripped into the mixed solution containing 3, 4-ethylenedioxythiophene and stirred for 12 hours at 30 ℃; washing the obtained product to be neutral by using deionized water, centrifuging to obtain a precipitate, dispersing the precipitate into 20mL of deionized water, adding 1.5mL of hydrofluoric acid, stirring for 3 hours, washing to be neutral, and centrifuging to obtain hollow PEDOT;
(4) Dissolving the hollow PEDOT obtained in the step (3) in 20mL of ethylene glycol, adding 0.128g of thioacetamide, and stirring to dissolve the thioacetamide; 0.128g of antimony trichloride and 0.136g of bismuth nitrate pentahydrate are weighed, dissolved in 20mL of ethylene glycol and stirred to form a uniform mixed solution; mixing the two solutions together, stirring for 1h, adding 0.03g of lipoic acid, continuously stirring for 2h, then transferring into a hydrothermal kettle, and reacting at 60 ℃ for 24h; washing the obtained product with deionized water and ethanol for 3 times, and centrifuging to obtain Bi 0.67 Sb 1.33 S 3 PEDOT@LA composite material.
The Bi obtained is then reacted with 0.67 Sb 1.33 S 3 The PEDOT@LA composite electrode material was assembled into a potassium ion battery under the same conditions as in example 1. The assembled cells were tested for electrochemical performance at 0.5A/g for 100 cycles, with an initial specific discharge capacity higher than that of the material prepared in example 1, due to the main active component Bi 0.67 Sb 1.33 S 3 An increase in the amount of (2); after 100 cycles, the specific capacity slightly decreased due to Bi 0.67 Sb 1.33 S 3 The particles are enlarged, so that the mechanical stability of the material is deteriorated.
Example 3
(1) Mixing 10mL of water, 46mL of ethanol and 2mL of ammonia water, uniformly dispersing by ultrasonic, adding 2.2mL of tetraethoxysilane, stirring for 4 hours at 30 ℃, centrifuging the product at 7000r/min, washing the obtained precipitate with deionized water and ethanol for 3 times, and drying the washed product at 60 ℃ to obtain silica pellets; the diameter of the silica pellets is 150-250 nm;
(2) Taking 0.06g of the silica pellets obtained in the step (1), dispersing in 25mL of acetic acid by ultrasonic, adding 2.5mL of hydrogen peroxide, dispersing uniformly by ultrasonic, adding 0.5mL of 3-mercaptopropyl trimethoxy silane, stirring at 80 ℃ for 2 hours, washing the obtained product with deionized water to be neutral, and centrifuging to obtain modified silica pellets;
(3) Dissolving the modified silica pellets obtained in the step (2) in 6g of deionized water to form a mixed solution, transferring the mixed solution into 54g of deionized water, adding 0.3g of concentrated hydrochloric acid, uniformly dispersing by ultrasonic, adding 0.12g of 3, 4-ethylenedioxythiophene, and uniformly dispersing by ultrasonic; weighing 0.22g of ammonium persulfate to be dissolved in 5g of deionized water, slowly dropwise adding the ammonium persulfate solution into a mixed solution containing 3, 4-ethylenedioxythiophene, and stirring at 30 ℃ for 12 hours; washing the obtained product to be neutral by using deionized water, centrifuging to obtain a precipitate, dispersing the precipitate into 20mL of deionized water, adding 1.8mL of hydrofluoric acid, stirring for 3 hours, washing to be neutral, and centrifuging to obtain hollow PEDOT;
(4) Dissolving the hollow PEDOT obtained in the step (3) in 30mL of ethylene glycol, adding 0.085g of thioacetamide, and stirring to dissolve the thioacetamide; 0.086g of antimony trichloride and 0.091g of bismuth nitrate pentahydrate are weighed, dissolved in 20mL of ethylene glycol and stirred to form a uniform mixed solution; mixing the two solutions together, stirring for 1h, adding 0.04g of lipoic acid, continuously stirring for 2h, then transferring into a hydrothermal kettle, and reacting at 60 ℃ for 24h; washing the obtained product with deionized water and ethanol for 3 times, and centrifuging to obtain Bi 0.67 Sb 1.33 S 3 PEDOT@LA composite material.
The Bi obtained is then reacted with 0.67 Sb 1.33 S 3 The PEDOT@LA composite electrode material was assembled into a potassium ion battery under the same conditions as in example 1. The electrochemical performance of the assembled battery is tested, after 100 cycles at 0.5A/g, the specific discharge capacity is lower than that of the material prepared in the example 1, but the capacity retention rate is higher, and the addition of PEDOT and LA is proved to be capable of improving the mechanical performance of the material, effectively inhibiting the volume expansion problem of the material and improving the cycle performance of the material.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (6)
1. Bi (Bi) 0.67 Sb 1.33 S 3 The preparation method of the PEDOT@LA composite material is characterized by comprising the following steps of:
(1) Preparing silica pellets;
(2) Carrying out surface modification on the silica pellets prepared in the step (1);
(3) The 3, 4-ethylenedioxythiophene is polymerized to generate poly 3, 4-ethylenedioxythiophene and is uniformly coated on the surface of the silicon dioxide pellets, and the silicon dioxide pellets are completely etched by hydrofluoric acid to obtain hollow poly 3, 4-ethylenedioxythiophene;
(4) Antimony trichloride, bismuth nitrate pentahydrate, thioacetamide, lipoic acid and the poly-3, 4-ethylenedioxythiophene are reacted by a hydrothermal kettle to obtain a composite material Bi with the poly-3, 4-ethylenedioxythiophene as a matrix and loaded with antimony bismuth sulfide and lipoic acid 0.67 Sb 1.33 S 3 /PEDOT@LA；
The Bi is 0.67 Sb 1.33 S 3 The PEDOT@LA composite material has the structure that a hollow poly 3, 4-ethylenedioxythiophene network is coated with a layer of organic lipoic acid and loaded with antimony bismuth sulfide nano particles.
2. Bi as claimed in claim 1 0.67 Sb 1.33 S 3 The preparation method of the PEDOT@LA composite material is characterized by comprising the following steps of:
(1) Mixing water, ethanol and ammonia water, uniformly dispersing by ultrasonic waves, adding tetraethoxysilane, stirring for 3-4 hours at 30-40 ℃, centrifuging a product, washing the obtained precipitate with deionized water and ethanol for 3-5 times, and drying the washed product to obtain silica pellets;
(2) Taking the silica pellets obtained in the step (1), dispersing in acetic acid by ultrasonic, adding hydrogen peroxide, dispersing uniformly by ultrasonic, adding 3-mercaptopropyl trimethoxysilane, stirring at 80 ℃ for 2-2.5 h, washing the obtained product with deionized water to be neutral, and centrifuging to obtain modified silica pellets;
(3) Dissolving the modified silica pellets obtained in the step (2) in deionized water to form a mixed solution, transferring the mixed solution into the deionized water, adding concentrated hydrochloric acid, performing ultrasonic dispersion uniformly, adding 3, 4-ethylenedioxythiophene, and performing ultrasonic dispersion uniformly; dissolving ammonium persulfate in deionized water, slowly dropwise adding an ammonium persulfate solution into a mixed solution containing 3, 4-ethylenedioxythiophene, stirring at 30 ℃ for 12-13 h, washing the obtained product with deionized water to be neutral, centrifuging to obtain a precipitate, dispersing the precipitate into the deionized water, adding hydrofluoric acid, stirring for 3h, washing to be neutral, and centrifuging to obtain hollow poly-3, 4-ethylenedioxythiophene;
(4) Dissolving the hollow poly 3, 4-ethylenedioxythiophene obtained in the step (3) in ethylene glycol, adding thioacetamide, and stirring to dissolve the thioacetamide; dissolving antimony trichloride and bismuth nitrate pentahydrate in ethylene glycol, and stirring to form a uniform mixed solution; mixing the two solutions together, stirring for 0.5-1 h, adding lipoic acid, continuously stirring for 1-2 h, then transferring into a hydrothermal kettle, and reacting at 60 ℃ for 22-24 h; washing the obtained product with deionized water and ethanol for 3-5 times, and centrifuging to obtain Bi 0.67 Sb 1.33 S 3 PEDOT@LA composite material.
3. Bi as claimed in claim 2 0.67 Sb 1.33 S 3 The preparation method of the PEDOT@LA composite material is characterized in that in the step (1), the volume ratio of water to ethanol to ammonia water is (4-6): (20-23): 1, the volume ratio of tetraethoxysilane to ammonia water is (1.1-1.3), and the centrifugal rotating speed is 7000-9000 r/min.
4. Bi as claimed in claim 1 or 2 0.67 Sb 1.33 S 3 The preparation method of the PEDOT@LA composite material is characterized in that in the step (2), the mass volume ratio of the silica pellets to the 3-mercaptopropyl trimethoxysilane is (1-1.2) g 10mL.
5. As claimed in claim 1 or 2The Bi is 0.67 Sb 1.33 S 3 The preparation method of the PEDOT@LA composite material is characterized in that in the step (3), the mass ratio of 3, 4-ethylenedioxythiophene to concentrated hydrochloric acid to ammonium persulfate is 1 (2.4-2.6) (1.8-1.9), and the mass volume ratio of the silica pellets to hydrofluoric acid is 0.1g (2.8-3.2) mL.
6. Bi as claimed in claim 1 or 2 0.67 Sb 1.33 S 3 The preparation method of the PEDOT@LA composite material is characterized in that in the step (4), the mass ratio of poly (3, 4-ethylenedioxythiophene), lipoic acid and thioacetyl is 1 (2.5-3): (4-6), and the molar ratio of antimony trichloride to bismuth nitrate pentahydrate is (1.8-2.2): 1.
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