CN114899388B - Bismuth alkene/graphene composite material and preparation method and application thereof - Google Patents
Bismuth alkene/graphene composite material and preparation method and application thereof Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 89
- -1 Bismuth alkene Chemical class 0.000 title claims abstract description 62
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 239000006228 supernatant Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 7
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 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 claims description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910001414 potassium ion Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 239000002135 nanosheet Substances 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract 2
- 239000005457 ice water Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction 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
- H01M4/38—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/027—Negative 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 provides a bismuth-graphene/graphene composite material, a preparation method and application thereof, wherein metal bismuth powder is added into a solvent to obtain a mixed solution; ultrasonically and centrifugally collecting the mixed solution in an ice water bath to obtain a supernatant; adding a reducing agent into the supernatant, centrifuging, washing, and vacuum freeze-drying to obtain pure-phase bismuth alkene nano-sheets; dispersing the obtained bismuth alkene into deoxidized deionized water, mixing with graphene oxide, uniformly dispersing by ultrasonic, and performing vacuum filtration and film drawing; and (3) placing the obtained film into a liner of a reaction kettle, and adding a reducing agent for reaction to obtain the bismuth alkene/graphene composite material. The two-dimensional bismuth alkene in the composite material has an ultrathin lamellar structure, the thickness of the bismuth alkene is 0.5-2nm, and the bismuth alkene is compounded with graphene to form a film, so that the composite material is loose and porous. The obtained composite material has large specific surface area, can be fully contacted and infiltrated with electrolyte, has excellent flexibility, can relieve the volume expansion of the metal bismuth in the charge and discharge process, and improves the multiplying power performance and the cycle stability of the material.
Description
Technical Field
The invention relates to a bismuth alkene/graphene composite material, and a preparation method and application thereof, and belongs to the technical field of potassium ion batteries.
Background
In the last two decades, the lithium ion battery industry has evolved rapidly, and many people focus on and study lithium ion batteries. The life of people is full of various lithium ion batteries, such as: cell phones, automobiles, toys, etc. However, the distribution of lithium resources throughout the world is quite uneven (mainly concentrated in south america), and the abundance of lithium resources is not high. This results in higher and higher prices for lithium resources, making the advantages of their energy storage field less obvious. For these reasons, more and more people are turning to the study of potassium in the same main group as lithium. K/K + Is low, and the cell voltage and the cell energy density are high; k (K) + Weak interaction with solvent molecules, and the solvated potassium ions have smaller Stokes radius, so that K + The diffusion rate in the electrolyte solution is fast and the molar conductivity is good. The potassium ion battery starts to gradually replace the lithium ion battery, and becomes a new development direction in the energy storage field. The alloy type electrode has the advantage of high theoretical specific capacity and is concerned by researchers. Research into two-dimensional materials is gradually expanding from disulfides to the fifth main group. Wherein, the alloy type cathode material bismuth (Bi) has 382mAhg -1 Is a theoretical specific capacity of (c). However, in the bismuth alloying/dealloying process, the problem of volume expansion of bismuth is prominent, and active substances are easy to pulverize and fall off, so that the battery cycle stability is greatly reduced.
China's bismuth reserves are the first world, china has absolute advantages for bismuth. Bismuth is used as safe green metal and may be used in medicine, chemical industry, electronic industry, etc. Bismuth alkene has low thermal conductivity, and can be used for thermoelectric materials. Bismuth alkene has a wrinkled lamellar crystal structure, consists of six-membered rings, and larger interlayer channels (3.979A) are beneficial to ion deintercalation with large radius. The bismuth-antimony-based expansion problem can be solved by a bismuth-alkene method, and further the battery performance is improved. Moreover, a method for preparing the anode material of the potassium ion battery, which is simple in synthesis and easy to operate, does not exist so far, and can provide reference value for preparing other anode materials.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides the bismuth-graphene composite material, the preparation method and the application thereof, and the bismuth-graphene composite material is membranous, loose and porous and flexible, can effectively relieve the volume expansion of bismuth in the charge and discharge process, increase the contact area with electrolyte and greatly improve the electrochemical performance of a battery.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the bismuth alkene/graphene composite material comprises the following steps:
(1) Firstly placing metal bismuth powder into a container, adding a solvent into the container, carrying out ultrasonic grinding in a cold water bath, and then centrifugally collecting supernatant;
(2) Adding a reducing agent into the supernatant obtained in the step (1) for obtaining pure-phase bismuth alkene nanosheets, continuously stirring, centrifuging, washing and performing vacuum freeze drying to obtain bismuth alkene;
(3) Dispersing the bismuth alkene obtained in the step (2) into deoxidized deionized water, mixing with graphene oxide, uniformly dispersing by ultrasonic, and performing vacuum filtration and film drawing to obtain a film;
(4) And (3) putting the film obtained by suction filtration into a liner of a reaction kettle, and then adding a reducing agent for reaction to obtain the bismuth alkene/graphene composite material.
The step (2) is to add the reducing agent because bismuth metal powder is oxidized and Bi is converted into BiO when ultrasonic powder stripping is carried out x . Step (3) dispersing the bismuth alkene in de-ionized water for oxygen removal, and also for preventing the bismuth alkene from being oxidized.
Further, in the step (1), based on 0.5g of metal bismuth powder, transferring the metal bismuth powder into a container, adding 200mL solvent, and carrying out ultrasonic treatment for a period of time: 8-30h. The solvent is one or a mixture of two of deionized water and N-methyl pyrrolidone, and the centrifugal speed is 300-2000 rpm.
Further, the reducing agent in the step (2) is one or more of hydrazine hydrate, sodium borohydride, formaldehyde, ethylene glycol, ascorbic acid, isopropanol and glucose. The amount of reducing agent is such that the solution turns black and is slightly excessive.
Further, the centrifugal speed in the step (2) is 3000-20000 rpm, and the washing agent is deionized water or ethanol.
Further, the deionized water deoxidized in the step (3) adopts Ar or N which is introduced for 10min 2 Removing oxygen in water to obtain the bismuth alkene and graphene oxide with the mass ratio of (2-5): 1, and the ultrasonic time is 4-10h. Bismuth and graphene require vacuum drying.
Further, in the step (4), the mass ratio of the film to the reducing agent is 1: (1-4).
Further, the reaction temperature in the step (4) is 80-150 ℃ and the reaction time is 8-18h.
Further, the reducing agent in the step (4) is one or more of hydrazine hydrate, sodium borohydride, formaldehyde, ethylene glycol, ascorbic acid, isopropanol, N-methyl pyrrolidone and glucose.
The two-dimensional bismuth alkene in the bismuth alkene/graphene composite material prepared by the preparation method disclosed by the invention has an ultrathin lamellar structure, the thickness of the bismuth alkene is 0.5-2nm, and the bismuth alkene and the graphene are compounded into a film, so that the bismuth alkene/graphene composite material is loose and porous.
The bismuth alkene/graphene composite material disclosed by the invention is applied to a cathode material of a potassium ion battery.
The beneficial effects of the invention are as follows:
(1) The composite material obtained by the method is loose and porous, and is favorable for full contact and infiltration of the anode material and electrolyte. The bismuth graphene/graphene material with small thickness, large specific surface area and excellent flexibility can be prepared, so that the volume expansion of the metal bismuth in the charge and discharge process is effectively relieved, the problem of pulverization of the cathode material is solved, and the electrochemical performance of the material is improved.
(2) The bismuth alkene/graphene material prepared by the invention has the advantages of uniform size dispersion, complete structure and similar particle size.
(3) Compared with other methods, the bismuth alkene prepared by the method has thinner thickness.
(4) No additional current collector is needed and can be used as a self-supporting electrode.
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 described below. It is evident that the drawings in the following description are only some embodiments of the present invention and that other drawings may be obtained from these drawings by those of ordinary skill in the art without inventive effort.
FIG. 1 is an X-ray diffraction pattern of bismuth alkene prepared in example 1.
Fig. 2 is an X-ray diffraction pattern of the bismuth/graphene prepared in example 1.
FIG. 3 is a scanning electron microscope image of bismuth alkene prepared in example 1.
Fig. 4 is an atomic force microscope image of bismuth/graphene prepared in example 1.
FIG. 5 is an elemental distribution diagram of bismuth alkene prepared in example 1.
Fig. 6 is an elemental distribution diagram of the bismuth alkene/graphene composite material prepared in example 1.
Fig. 7 is a digital photograph of the bismuth alkene/graphene composite material prepared in example 1.
FIG. 8 is a cycle performance curve of the bismuth/graphene composite material prepared in example 1.
Detailed Description
The technical scheme of the invention will be described in detail below with reference to the accompanying drawings and examples. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation steps of the bismuth alkene/graphene composite material negative electrode material in the embodiment are as follows:
(1) Placing 0.5g of metal bismuth powder into a container, adding 200mL deionized water, performing ultrasonic treatment in a cold water bath for 30 hours, centrifuging at 500rpm, and collecting supernatant;
(2) Adding 17.5mL of reducing agent sodium borohydride solution into the supernatant obtained in the step (1), and continuously stirring until the solution is not discolored;
(3) Centrifuging the liquid in the step (2) at 10000rpm, washing with deionized water and absolute ethyl alcohol for 2 times respectively, and vacuum freeze-drying;
(4) Introducing Ar into deionized water for 10min to remove oxygen in the water, adding the bismuth alkene obtained in the step (3) into the deoxygenated deionized water, mixing graphene oxide and bismuth alkene in a mass ratio of 1:4, performing ultrasonic dispersion for 5h, performing vacuum filtration and film drawing, and performing vacuum drying on the bismuth alkene/graphene;
(5) And (3) putting the film obtained by suction filtration into a liner of a reaction kettle, then adding hydrazine hydrate, and determining the dosage of the hydrazine hydrate according to the mass ratio of the film to the hydrazine hydrate of 1:2. Reacting for 10 hours at 80 ℃ to obtain the target product.
Analysis and test of morphology and electrochemical performance are respectively carried out on the sample in the example 1, and the result shows that the prepared sample shows excellent electrochemical performance.
As shown in fig. 3, the prepared bismuth alkene has an ultrathin lamellar structure and a large specific surface area, is favorable for fully contacting and soaking electrolyte and a cathode material, and effectively relieves the volume expansion of the battery in the charge and discharge process.
As shown in FIG. 4, the prepared bismuth alkene has an ultrathin lamellar structure, and the thickness is 0.5-2 nanometers.
As shown in fig. 6, bismuth and carbon in the prepared bismuth-graphene composite material are uniformly distributed, which is beneficial to electron conduction and volume expansion relief.
As shown in fig. 7, the prepared bismuth alkene/graphene composite material has good flexibility, and is beneficial to alleviating the problem of volume expansion.
FIG. 8 is a schematic diagram of the prepared bismuth/graphene composite material as a self-supporting negative electrode of a potassium ion batteryCycle performance curve. The test results show that: in the voltage range of 0.01-3.0V, 1A g -1 The initial reversible specific capacity of the electrode material is 224.9mA h g under the current density -1 After 500 charge and discharge cycles, the capacity retention rate was 93.5%, and the material exhibited excellent cycle performance.
Example 2
The preparation steps of the bismuth alkene/graphene composite material negative electrode material in the embodiment are as follows:
(1) Putting 0.5g of metal bismuth powder into a container, adding 200mL deionized water, performing ultrasonic treatment in a cold water bath for 25 hours, centrifuging at 1000rpm, and collecting supernatant;
(2) Adding 15mL of reducing agent sodium borohydride solution into the supernatant obtained in the step (1), and continuously stirring until the solution is no longer colored;
(3) Centrifuging the liquid in the step (2) at 8000rpm, washing with deionized water and absolute ethyl alcohol for 2 times respectively, and vacuum freeze-drying;
(4) Introducing Ar into deionized water for 20min to remove oxygen in the water, adding the bismuth alkene obtained in the step (3) into the deoxygenated deionized water, mixing graphene oxide and bismuth alkene in a mass ratio of 1:3, performing ultrasonic dispersion for 7h, performing vacuum filtration and film drawing, and performing vacuum drying on the bismuth alkene/graphene;
(5) And (3) putting the film obtained by suction filtration into a liner of a reaction kettle, then adding ethylene glycol, and determining the dosage of the ethylene glycol according to the mass ratio of the film to the ethylene glycol of 1:2. Reacting for 10 hours at 100 ℃ to obtain the target product.
Analysis and test of morphology and electrochemical performance are respectively carried out on the sample in the example 2, and the result shows that the prepared sample has excellent capacity retention capability and better electrochemical performance.
Example 3
The preparation steps of the bismuth alkene/graphene composite material negative electrode material in the embodiment are as follows:
1) Putting 0.5g of metal bismuth powder into a container, adding 200 mLN-methyl pyrrolidone, performing cold water bath ultrasonic treatment for 30 hours, centrifuging at 800rpm, and collecting supernatant;
(2) Adding 20mL of reducing agent hydrazine hydrate into the supernatant obtained in the step (1), and continuously stirring until the solution is not discolored;
(3) Centrifuging the liquid in the step (2) at 5000rpm, washing with deionized water and absolute ethyl alcohol for 2 times respectively, and vacuum freeze-drying;
(4) Will N 2 Introducing deionized water for 10min to remove oxygen in the water, adding the bismuth alkene obtained in the step (3) into the deoxygenated deionized water, mixing the graphene oxide and the bismuth alkene in a mass ratio of 1:5, performing ultrasonic dispersion for 7h, performing vacuum filtration and film drawing, and performing vacuum drying on the bismuth alkene/graphene;
(5) And (3) putting the film obtained by suction filtration into a liner of a reaction kettle, then adding isopropanol, and determining the dosage of the isopropanol according to the mass ratio of the film to the isopropanol of 1:2. Reacting for 15 hours at 150 ℃ to obtain the target product.
Analysis and test of morphology and electrochemical performance are respectively carried out on the sample in the example 3, and the result shows that the prepared sample has excellent capacity retention capability and better electrochemical performance.
Example 4
The preparation steps of the bismuth alkene/graphene composite material negative electrode material in the embodiment are as follows:
1) Putting 0.5g of metal bismuth powder into a container, adding 200mL of N-methylpyrrolidone, performing cold water bath ultrasonic treatment for 10 hours, centrifuging at 500rpm, and collecting supernatant;
(2) Adding 30mL of reducing agent sodium borohydride into the supernatant obtained in the step (1), and continuously stirring until the solution is not discolored;
(3) Centrifuging the liquid in the step (2) at 10000rpm, washing with deionized water and absolute ethyl alcohol for 2 times respectively, and vacuum freeze-drying;
(4) Will N 2 Introducing deionized water for 10min to remove oxygen in the water, adding the bismuth alkene obtained in the step (3) into the deoxygenated deionized water, mixing graphene oxide and bismuth alkene in a mass ratio of 1:2, and performing ultrasonic treatmentDispersing for 10 hours, performing vacuum filtration and film drawing, and performing vacuum drying on the bismuth graphene/graphene;
(5) And (3) putting the film obtained by suction filtration into a liner of a reaction kettle, then adding formaldehyde, and determining the dosage of the formaldehyde according to the mass ratio of the film to the formaldehyde of 1:1. Reacting for 6 hours at 80 ℃ to obtain the target product.
Analysis and test of morphology and electrochemical performance are respectively carried out on the sample in the example 4, and the result shows that the prepared sample has excellent capacity retention capability and better electrochemical performance.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (6)
1. The preparation method of the bismuth alkene/graphene composite material is characterized by comprising the following steps:
(1) Firstly placing metal bismuth powder into a container, adding a solvent, carrying out ultrasonic grinding in a cold water bath, then centrifuging to collect supernatant, transferring the supernatant into the container based on 0.5g of metal bismuth powder, adding 200mL solvent, and carrying out ultrasonic treatment for the time: 8-30h; the solvent is one or a mixture of two of deionized water and N-methyl pyrrolidone, and the centrifugal speed is 300-2000 rpm;
(2) Adding a reducing agent into the supernatant obtained in the step (1), continuously stirring, centrifuging, washing, and performing vacuum freeze drying to obtain bismuth alkene;
(3) Dispersing the bismuth alkene obtained in the step (2) into deoxidized deionized water, mixing with graphene oxide, uniformly dispersing by ultrasonic, and performing vacuum filtration and film drawing to obtain a film;
(4) Putting the film obtained by suction filtration into a liner of a reaction kettle, wherein the mass ratio of the film to the reducing agent is 1: (1-4), adding a reducing agent for reaction, wherein the reaction temperature is 80-180 ℃, the reaction time is 8-18h, and the bismuth alkene/graphene composite material is obtained, wherein the two-dimensional bismuth alkene in the composite material has an ultrathin lamellar structure, the thickness of the bismuth alkene is 0.5-2nm, and the bismuth alkene and the graphene are compounded into a film, so that the film is loose and porous.
2. The method for preparing the bismuth alkene/graphene composite material according to claim 1, wherein: the reducing agent in the step (2) is one or more than one of hydrazine hydrate, sodium borohydride, formaldehyde, ethylene glycol, ascorbic acid, isopropanol and glucose.
3. The method for preparing the bismuth alkene/graphene composite material according to claim 1, wherein: the centrifugal speed in the step (2) is 3000-20000 rpm, and the washing agent used for washing is deionized water or ethanol.
4. The method for preparing the bismuth alkene/graphene composite material according to claim 1, wherein: the deionized water deoxidized in the step (3) adopts Ar or N which is introduced for 10min 2 Removing oxygen in water to obtain the bismuth-graphene composite material, wherein the mass ratio of bismuth-graphene to graphene is (2-5): 1, and the ultrasonic time is 4-10h.
5. The method for preparing the bismuth alkene/graphene composite material according to claim 1, wherein: the reducing agent in the step (4) is one or more than one of hydrazine hydrate, sodium borohydride, formaldehyde, ethylene glycol, ascorbic acid, isopropanol and glucose.
6. The use of the bismuth alkene/graphene composite material of claim 1 as a negative electrode material of a potassium ion battery.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106410128A (en) * | 2016-07-18 | 2017-02-15 | 苏州大学 | Preparation method of graphene-bismuth oxide composite material for lithium ion battery negative electrode |
| CN107026263A (en) * | 2017-06-02 | 2017-08-08 | 扬州大学 | Sea urchin shape bismuth sulfide/macropore graphene composite material, preparation method and applications |
| CN111668471A (en) * | 2020-06-23 | 2020-09-15 | 商丘师范学院 | Antimony/graphene composite material for potassium ion battery cathode and preparation method thereof |
| CN112209437A (en) * | 2020-10-16 | 2021-01-12 | 南开大学 | Preparation method of bismuth sulfide nano particle and graphene composite material |
| CN113087016A (en) * | 2021-04-06 | 2021-07-09 | 浙江加州国际纳米技术研究院台州分院 | Preparation method of rod-shaped bismuth sulfide/reduced graphene oxide composite material |
| CN113130908A (en) * | 2021-04-20 | 2021-07-16 | 安徽大学 | Bismuth antimony telluride/graphene potassium ion battery cathode material with high-stability structure and preparation method thereof |
Family Cites Families (1)
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106410128A (en) * | 2016-07-18 | 2017-02-15 | 苏州大学 | Preparation method of graphene-bismuth oxide composite material for lithium ion battery negative electrode |
| CN107026263A (en) * | 2017-06-02 | 2017-08-08 | 扬州大学 | Sea urchin shape bismuth sulfide/macropore graphene composite material, preparation method and applications |
| CN111668471A (en) * | 2020-06-23 | 2020-09-15 | 商丘师范学院 | Antimony/graphene composite material for potassium ion battery cathode and preparation method thereof |
| CN112209437A (en) * | 2020-10-16 | 2021-01-12 | 南开大学 | Preparation method of bismuth sulfide nano particle and graphene composite material |
| CN113087016A (en) * | 2021-04-06 | 2021-07-09 | 浙江加州国际纳米技术研究院台州分院 | Preparation method of rod-shaped bismuth sulfide/reduced graphene oxide composite material |
| CN113130908A (en) * | 2021-04-20 | 2021-07-16 | 安徽大学 | Bismuth antimony telluride/graphene potassium ion battery cathode material with high-stability structure and preparation method thereof |
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