CN113921790A - Bimetal selenide negative electrode material and preparation method and application thereof - Google Patents
Bimetal selenide negative electrode material and preparation method and application thereof Download PDFInfo
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- CN113921790A CN113921790A CN202111172161.5A CN202111172161A CN113921790A CN 113921790 A CN113921790 A CN 113921790A CN 202111172161 A CN202111172161 A CN 202111172161A CN 113921790 A CN113921790 A CN 113921790A
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- 150000003346 selenoethers Chemical class 0.000 title claims abstract description 51
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 17
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000001291 vacuum drying Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 235000014101 wine Nutrition 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 25
- -1 amine salt Chemical class 0.000 claims description 13
- 150000002815 nickel Chemical class 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 5
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 239000012991 xanthate Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 abstract description 7
- 230000001351 cycling effect Effects 0.000 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 229910052711 selenium Inorganic materials 0.000 description 7
- 239000011669 selenium Substances 0.000 description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- PYHYDDIOBZRCJU-UHFFFAOYSA-N [Ni]=[Se].[Co] Chemical compound [Ni]=[Se].[Co] PYHYDDIOBZRCJU-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical group COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960000686 benzalkonium chloride Drugs 0.000 description 1
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 235000020095 red wine Nutrition 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical group [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—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
- H01M4/58—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
-
- 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 discloses a bimetallic selenide negative electrode material and a preparation method and application thereof, metal salt and a surfactant are added into a mixed solution of methanol and deionized water, and a wine red solution is obtained by stirring; heating the prepared wine red solution, naturally cooling, centrifuging, washing and vacuum drying to obtain a precursor; and mixing the precursor and selenium powder in an inert atmosphere, and then carrying out low-temperature annealing treatment to obtain the bimetallic selenide. The lithium ion battery cathode material has high specific discharge capacity, good multiplying power and cycling stability, and shows great potential as a sodium ion battery cathode material.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a bimetallic selenide negative electrode material as well as a preparation method and application thereof.
Background
The development of rechargeable batteries to replace fossil fuels has attracted considerable attention in recent years. Although lithium ion batteries have been commercially successful, the scarcity and high cost of lithium have severely hampered their use in large devices and electric vehicles. Sodium ion batteries are considered to be ideal next-generation rechargeable batteries because they have electrochemical performance comparable to that of lithium ion batteries and use abundant sodium as an energy storage medium.
However, the large radius of sodium ions limits their kinetic performance, preventing their commercial application. To date, a variety of anode materials for sodium ion batteries have been studied, including carbon-based materials, metal oxides, phosphides, sulfides, and the like. However, carbon-based materials, such as graphite, have a reversible capacity of only about 300mAh g-1 in sodium ion batteries and suffer from sodium dendrite growth. The decomposition of sodium oxide formed after the discharge of the metal oxide is extremely difficult, and the reversibility of the battery is poor. And the poor stability of phosphide limits the improvement of the cycle performance of the battery.
Disclosure of Invention
The invention aims to solve the technical problem of providing a bimetallic selenide negative electrode material and a preparation method and application thereof aiming at the defects in the prior art, the novel bimetallic selenide negative electrode material is synthesized by adopting a hydrothermal and low-temperature heat treatment two-step method, and compared with the traditional selenide, the novel bimetallic selenide negative electrode material has higher specific discharge capacity and good cycling stability, and shows great potential as a sodium ion battery negative electrode material.
The invention adopts the following technical scheme:
a method for preparing a bimetal selenide negative electrode material comprises the steps of adding metal salt and a surfactant into a mixed solution of methanol and deionized water, and stirring to obtain a wine red solution; heating the prepared wine red solution, naturally cooling, centrifuging, washing and vacuum drying to obtain a precursor; and mixing the precursor and selenium powder in an inert atmosphere, and then carrying out low-temperature annealing treatment to obtain the bimetallic selenide.
Specifically, the metal salt comprises nickel salt and cobalt salt, and the addition ratio of the nickel salt to the cobalt salt is (0.5-2): 1.
specifically, the volume ratio of methanol to deionized water is (0.2-5): 1.
specifically, the surfactant is one or more of an amine salt type, a quaternary ammonium salt type, a heterocyclic type and a xanthate type.
Specifically, the addition amount of the surfactant is 0.5-1 g.
Specifically, the prepared wine red solution is heated to 100-180 ℃, and naturally cooled after being continuously heated for 10-20 hours.
Specifically, the temperature of the low-temperature annealing treatment is 300-450 ℃, and the annealing time is 0.5-3 h.
Specifically, the mass ratio of the precursor to the selenium powder is (0.5-1): 1.
the other technical scheme of the invention is that the current density of the bimetal selenide negative electrode material is 20A g-1The cycle time is 1300 to 1600 cycles, and the specific capacity is 553 to 373mAh g-1。
The invention also provides the application of the bimetallic selenide negative electrode material in the sodium-ion battery.
Compared with the prior art, the invention has at least the following beneficial effects:
the preparation method of the bimetallic selenide negative electrode material, disclosed by the invention, has the advantages that the precursor is synthesized by a hydrothermal method, and then the bimetallic selenide material is obtained through low-temperature heat treatment, so that the cost is low, the preparation process is simple, the material structure is stable, the repeatability is good, and the bimetallic selenide negative electrode material can be produced in a large scale.
Further, in the process of preparing the bimetallic selenide, the flaky precursor is obtained by regulating and controlling the proportion and the concentration of the nickel salt and the cobalt salt and the amount of the surfactant thereof.
Further, because the precursor lamella that adopts water to prepare as the solvent alone is thicker, and the follow-up process is difficult to the selenization, therefore we adopt methanol to regulate and control lamella thickness, and the ratio range of methanol and water that the experimentation was explored is 0.2 ~ 5: 1.
furthermore, because the precursor prepared by simply adopting the metal salt is easy to agglomerate and is difficult to selenize in the subsequent process, the surfactant is adopted to reduce the surface energy of the nano-particles and inhibit the agglomeration of the nano-particles.
Furthermore, a small amount of surfactant cannot sufficiently inhibit the agglomeration of the nanoparticles, but the excessive surfactant can increase the thickness of the nanosheet layer, and the addition amount of the surfactant searched in the experimental process is 0.5-1 g.
Further, in the process of preparing the precursor, the solution heat treatment temperature is too low, the time is too short, and a flaky precursor with good crystallinity is difficult to generate; too high heat treatment temperature and too long heat treatment time lead to the cracking and agglomeration of the sheet layer shape, which is not favorable for the smooth proceeding of the selenization process in the later period. Therefore, the heating temperature of the precursor is limited to be 100-180 ℃, and the time is 10-20 hours.
Furthermore, in order to obtain the nickel-cobalt double-metal selenide material with excellent performance, the proportion of the precursor to the selenide is too high, the heat treatment time is too long, so that pure-phase nickel-cobalt selenide can be directly generated, the proportion is too low, the heat treatment time is too short, so that a large amount of agglomerated metal selenium can wrap the precursor inside, and the selenization degree is not enough, so that the selenization temperature in the selenization process obtained through the experiment is 300-450 ℃, and the selenization time is 0.5-3 h.
Further, in order to obtain the nickel-cobalt double-metal selenide material with excellent performance, the proportion of the precursor to the selenide is too high, the heat treatment time is too long, so that pure-phase nickel-cobalt selenide can be directly generated, the proportion is too low, the heat treatment time is too short, so that a large amount of agglomerated metal selenium can wrap the precursor inside, and the selenization degree is not enough, so that the ratio of the precursor to the selenium in the selenization process finally obtained through tests is 0.5-1.
The finally prepared bimetallic selenide negative electrode material has a porous structure, wherein a nickel-cobalt selenide compound core and a shell wrapped by monodisperse selenium particles are applied to the negative electrode material of the sodium-ion battery, so that the bimetallic selenide negative electrode material has excellent discharge capacity, rate capability and long-term circulation stability, and has good application prospect in developing a cheap high-performance sodium-ion battery system.
In conclusion, the bimetallic selenide prepared by the simple preparation process and the regulation and control of experimental parameters shows excellent electrochemical performance when used as the cathode material of the sodium-ion battery, and has good application prospect.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is an SEM image of a precursor prepared in example 1;
fig. 2 is an SEM image of the double metal selenide prepared in example 1;
fig. 3 is an SEM image of the dual metal selenide prepared in example 5;
fig. 4 is a graph showing a rate test of the double metal selenide prepared in example 1;
fig. 5 is a graph comparing the cycles of the double metal selenides prepared in example 1 and comparative example 1.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the present invention, all the embodiments and preferred methods mentioned herein can be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, the percentage (%) or parts means the weight percentage or parts by weight with respect to the composition, if not otherwise specified.
In the present invention, the components referred to or the preferred components thereof may be combined with each other to form a novel embodiment, if not specifically stated.
In the present invention, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "6 to 22" means that all real numbers between "6 to 22" have been listed herein, and "6 to 22" is simply a shorthand representation of the combination of these values.
The "ranges" disclosed herein may have one or more lower limits and one or more upper limits, respectively, in the form of lower limits and upper limits.
As used herein, the term "and/or" refers to any and all possible combinations of one or more of the associated listed items and includes such combinations.
In the present invention, unless otherwise specified, the individual reactions or operation steps may be performed sequentially or may be performed in sequence. Preferably, the reaction processes herein are carried out sequentially.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present invention.
The invention provides a bimetal selenide negative electrode material and a preparation method and application thereof, and a high-performance bimetal selenide consisting of a nickel-cobalt selenide compound core and a shell wrapped by monodisperse selenium particles is obtained by controlling the depth of a selenization process. The selenizing method regulates the particle size and the structure of the selenide by creating a liquid-phase selenizing environment, and the monodisperse selenium particles in the shell can play a role in improving the capacity and relieving the volume expansion; the prepared material is used for the sodium ion battery, has higher specific discharge capacity and good multiplying power and cycling stability, and shows great potential as a negative electrode material of the sodium ion battery.
The invention relates to a preparation method of a bimetallic selenide negative electrode material, which comprises the following steps:
s1, adding a first metal salt a, a second metal salt b and a surfactant into a mixed solution of methanol and deionized water, wherein the adding amount ratio of the first metal salt a to the second metal salt b is (0.5-2): 1, the volume ratio of methanol to deionized water is (0.2-5): 1, stirring to fully dissolve the red wine to obtain a wine red solution;
preferably, the first metal salt a is selected from nickel salt, and can be one or more of nitrate, chloride and sulfate; the second metal salt b is selected from cobalt salt, and can be one or more of nitrate, chloride and sulfate.
Preferably, the surfactant is one or more of an amine salt type, a quaternary ammonium salt type, a heterocyclic type and a xanthate type.
Preferably, the addition amount of the surfactant is 0.5 to 1 g.
S2, transferring the wine red solution prepared in the step S1 to a polytetrafluoroethylene reaction kettle; heating to 100-180 ℃, continuing for 10-20 h, and naturally cooling;
s3, centrifuging, washing and vacuum drying the solution cooled in the step S2 to obtain a precursor;
s4, under an inert atmosphere, mixing the precursor prepared in the step S3 and selenium powder, then placing the mixture in a tube furnace for low-temperature annealing at 300-450 ℃, wherein the annealing time is 0.5-3 h, and the mass ratio of the precursor to the selenium powder is (0.5-1): 1, preparing the bimetallic selenide.
The bimetal selenide negative electrode material prepared by the method of the invention has excellent electrochemical performance when being applied to a negative electrode material of a sodium-ion battery: current density of 20Ag-1The specific capacity is maintained at 553-373 mAh g after 1300-1600 cycles-1。
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Weighing 1.8mmol of nickel nitrate hexahydrate, 0.9mmol of cobalt nitrate hexahydrate and 1g of hexadecyl trimethyl ammonium bromide, dissolving in a mixed solution of 60mL of ethanol and 15mL of deionized water, and stirring for 30min to obtain a clear solution;
putting the solution into a reaction kettle with a 100mL polytetrafluoroethylene lining, reacting at 180 ℃ for 20h, naturally cooling, centrifuging, washing, and vacuum drying to obtain a precursor;
(2) weighing the precursor and the selenium powder according to the mass ratio of 1:2, pouring the precursor and the selenium powder into a mortar, manually grinding for 30min, and uniformly mixing. And (3) annealing the mixture at 350 ℃ for 3h under an inert atmosphere to obtain the bimetallic selenide.
Referring to figures 1 and 2 of the drawings,
example 2
(1) Weighing, adding 0.9mmol of nickel nitrate hexahydrate, 1.8mmol of cobalt nitrate hexahydrate and 1g of octadecyl dimethyl benzyl ammonium chloride, dissolving in a mixed solution of 15mL of ethanol and 60mL of deionized water, and stirring for 30min to obtain a clear solution;
putting the solution into a reaction kettle with a 100mL polytetrafluoroethylene lining, and reacting for 20h at 180 ℃; naturally cooling, centrifuging, washing, and vacuum drying to obtain precursor;
(2) weighing the precursor and the selenium powder according to the mass ratio of 1:2, pouring the precursor and the selenium powder into a mortar, manually grinding for 30min, and uniformly mixing. And (3) annealing the mixture at the low temperature of 300 ℃ for 3 hours under the inert atmosphere to obtain the bimetallic selenide.
Example 3
(1) 1.8mmol of nickel nitrate hexahydrate, 0.9mmol of cobalt nitrate hexahydrate and 0.5g of benzalkonium chloride are added and weighed, dissolved in a mixed solution of 60mL of ethanol and 15mL of deionized water, and stirred for 30min to obtain a clear solution;
putting the solution into a reaction kettle with a 100mL polytetrafluoroethylene lining, and reacting for 10h at 100 ℃; naturally cooling, centrifuging, washing, and vacuum drying to obtain precursor;
(2) weighing the precursor and the selenium powder according to the mass ratio of 1:1, pouring the precursor and the selenium powder into a mortar, manually grinding for 30min, and uniformly mixing; and (3) annealing the mixture at the low temperature of 450 ℃ for 0.5h under the inert atmosphere to obtain the bimetallic selenide.
Example 4
(1) Weighing, adding 0.9mmol of nickel nitrate hexahydrate, 1.8mmol of cobalt nitrate hexahydrate and 0.5g of cationic polyacrylamide into a mixed solution of 60mL of ethanol and 15mL of deionized water, and stirring for 30min to obtain a clear solution;
putting the solution into a reaction kettle with a 100mL polytetrafluoroethylene lining, and reacting for 10h at 100 ℃; naturally cooling, centrifuging, washing, and vacuum drying to obtain precursor;
(2) weighing the precursor and the selenium powder according to the mass ratio of 1:1, pouring the precursor and the selenium powder into a mortar, manually grinding for 30min, and uniformly mixing; and (3) annealing the mixture at the low temperature of 300 ℃ for 0.5h under the inert atmosphere to obtain the bimetallic selenide.
Example 5
(1) 1.8mmol of nickel nitrate hexahydrate, 0.9mmol of cobalt nitrate hexahydrate and 1g of hexadecyl trimethyl ammonium bromide are weighed and added into a mixed solution of 60mL of ethanol and 15mL of deionized water, and the mixture is stirred for 30min to obtain a clear solution;
putting the solution into a reaction kettle with a 100mL polytetrafluoroethylene lining, and reacting for 20h at 180 ℃; naturally cooling, centrifuging, washing and vacuum drying to obtain the precursor.
(2) Weighing the precursor and the selenium powder according to the mass ratio of 1:2, pouring the precursor and the selenium powder into a mortar, manually grinding for 30min, and uniformly mixing. And (3) annealing the mixture at 350 ℃ for 3h under an inert atmosphere to obtain the bimetallic selenide.
Choose to useThe bimetallic selenides prepared in the above examples were tested for electrochemical performance by assembling the materials into button half cells in a glove box. In the assembly of the half cell, a metal sodium sheet was used as a counter electrode, and 1.0M NaCF was contained3SO3The method comprises the steps of (the solvent is TETRAGLYME ═ 100 Vol% solution) using an electrolyte, uniformly mixing 70 wt% of active substance, 10 wt% of conductive carbon black and 10 wt% of polyvinylidene fluoride (PVDF) using N-methylpyrrolidone (NMP) as a solvent for a negative electrode, coating the mixture on a copper foil, putting the copper foil into a vacuum drying oven for vacuum drying for 12 hours at 110 ℃, naturally cooling to room temperature, putting a pole piece on a roller press for rolling, enabling the pole piece to be tightly attached to the copper foil, cutting the pole piece into 12mm round pieces by a cutting machine, weighing, putting the round pieces into a vacuum glove box, and assembling the half cell. After the assembly, the mixture is placed at room temperature and kept stand for 12 hours, and after the electrolyte is completely soaked, an electrochemical test is carried out, as shown in fig. 3.
Comparative example 1
(1) Weighing 1.8mmol of nickel nitrate hexahydrate, 0.9mmol of cobalt nitrate hexahydrate and 1g of hexadecyl trimethyl ammonium bromide, dissolving in a mixed solution of 60mL of ethanol and 15mL of deionized water, and stirring for 30min to obtain a clear solution;
putting the solution into a reaction kettle with a 100mL polytetrafluoroethylene lining, reacting at 180 ℃ for 20h, naturally cooling, centrifuging, washing, and vacuum drying to obtain a precursor;
(2) weighing the precursor and the selenium powder according to the mass ratio of 1:2, pouring the precursor and the selenium powder into a mortar, manually grinding for 30min, and uniformly mixing. And (3) annealing the mixture at 350 ℃ for 6h under an inert atmosphere to obtain the bimetallic selenide.
The bimetallic selenides prepared in the comparative examples were selected and tested for electrochemical performance by assembling the materials into button half cells in a glove box. In the assembly of the half cell, a metal sodium sheet was used as a counter electrode, and 1.0M NaCF was contained3SO3(solvent is TETRAGLYME ═ 100 Vol% solution) solution is used as electrolyte, N-methyl pyrrolidone (NMP) is used as solvent for negative electrode, 70 wt% of active substance, 10 wt% of conductive carbon black and 10 wt% of polyvinylidene fluoride (PVDF) are mixed uniformly, coated on copper foil, put into vacuum drying oven, and then dried at 110 deg.CAnd (4) drying for 12h, naturally cooling to room temperature, rolling the pole piece on a roller press to enable the pole piece to be tightly attached to the copper foil, cutting the pole piece into a 12mm wafer by a cutting machine, weighing, and then putting the wafer into a vacuum glove box for half-cell assembly. Standing at room temperature for 12h after the assembly, and carrying out electrochemical test after the electrolyte is completely soaked.
Referring to fig. 1, 2 and 4, the multiplying power performance diagram of the dual metal selenide negative electrode material is shown, the test voltage interval is 0.01-3V, and the current density is 0.5A-g-1Increased to 25A g-1When the current density is 0.5A · g-1The discharge capacity was 636.7mAh g-1When the current density is increased to 25A g-1The electrode can still provide 394.7mAh g-1Capacity. In addition, when the current density was recovered to 0.5A · g-1The reversible capacity can be recovered to 631.2mAh g-1And exhibits excellent reversibility.
Referring to FIG. 5, the cycle of the double metal selenides prepared in example 1 and comparative example 1 is compared, and the cycle of comparative example 1 is 20A g-1The reversible specific capacity after 1600 cycles under the current density is only 286.3mAh g-1And has a lower capacity. Example 1 at 20A g-1The reversible specific capacity after 1600 cycles under the current density is still kept at 373.0mAh g-1The capacity retention rate is 86.5%, and good cycle stability is shown.
In summary, the bimetal selenide negative electrode material and the preparation method and the application thereof of the invention can obtain the bimetal selenide negative electrode material with a porous structure through a simple preparation process, wherein the nickel-cobalt selenide compound core and the shell wrapped by the monodisperse selenium particles are applied to the negative electrode material of the sodium-ion battery at the temperature of 20 A.g-1The reversible specific capacity after 1600 cycles under the current density is still kept at 373.0mAh g-1The capacity retention rate was 86.5%. When the current density is increased to 25A g-1The electrode can still provide 394.7mAh g-1The capacity shows excellent discharge capacity, rate performance and long-term cycling stability, and has good application prospect in developing a cheap high-performance sodium ion battery system.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a bimetallic selenide negative electrode material is characterized in that metal salt and a surfactant are added into a mixed solution of methanol and deionized water, and are stirred to obtain a wine red solution; heating the prepared wine red solution, naturally cooling, centrifuging, washing and vacuum drying to obtain a precursor; and mixing the precursor and selenium powder in an inert atmosphere, and then carrying out low-temperature annealing treatment to obtain the bimetallic selenide.
2. The method according to claim 1, wherein the metal salt comprises a nickel salt and a cobalt salt, and the addition ratio of the nickel salt to the cobalt salt is (0.5-2): 1.
3. the method according to claim 1, wherein the volume ratio of the methanol to the deionized water is (0.2-5): 1.
4. the method according to claim 1, wherein the surfactant is one or more of an amine salt type, a quaternary ammonium salt type, a heterocyclic type and a xanthate type.
5. The method according to claim 1, wherein the surfactant is added in an amount of 0.5 to 1 g.
6. The method as claimed in claim 1, wherein the prepared wine red solution is heated to 100-180 ℃ for 10-20 h and then naturally cooled.
7. The method according to claim 1, wherein the low temperature annealing treatment is performed at a temperature of 300 to 450 ℃ for 0.5 to 3 hours.
8. The method according to claim 1, wherein the mass ratio of the precursor to the selenium powder is (0.5-1): 1.
9. the bi-metal selenide negative electrode material prepared by the method of claim 1, wherein the current density is 20Ag-1The cycle time is 1300 to 1600 cycles, and the specific capacity is 553 to 373mAh g-1。
10. Use of the bimetallic selenide negative electrode material prepared according to the method of claim 1 or the bimetallic selenide negative electrode material of claim 9 in a sodium ion battery.
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