CN114709357A - Antimony negative electrode and aqueous alkaline battery based on antimony negative electrode - Google Patents
Antimony negative electrode and aqueous alkaline battery based on antimony negative electrode Download PDFInfo
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- CN114709357A CN114709357A CN202210207562.8A CN202210207562A CN114709357A CN 114709357 A CN114709357 A CN 114709357A CN 202210207562 A CN202210207562 A CN 202210207562A CN 114709357 A CN114709357 A CN 114709357A
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- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 103
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- 238000000151 deposition Methods 0.000 claims description 24
- 230000008021 deposition Effects 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 12
- 239000004917 carbon fiber Substances 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 8
- -1 cation salt Chemical class 0.000 claims description 8
- 229940026189 antimony potassium tartrate Drugs 0.000 claims description 7
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 229910001245 Sb alloy Inorganic materials 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000002140 antimony alloy Substances 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 5
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000004070 electrodeposition Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- KGHMFMDJVUVBRY-UHFFFAOYSA-N antimony copper Chemical compound [Cu].[Sb] KGHMFMDJVUVBRY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000379 antimony sulfate Inorganic materials 0.000 claims description 2
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 claims description 2
- MVMLTMBYNXHXFI-UHFFFAOYSA-H antimony(3+);trisulfate Chemical compound [Sb+3].[Sb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MVMLTMBYNXHXFI-UHFFFAOYSA-H 0.000 claims description 2
- 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 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000011133 lead Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 description 14
- 229910001369 Brass Inorganic materials 0.000 description 9
- 239000010951 brass Substances 0.000 description 9
- 229910000411 antimony tetroxide Inorganic materials 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 7
- 238000011161 development Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- DYDCUQKUCUHJBH-UWTATZPHSA-N D-Cycloserine Chemical compound N[C@@H]1CONC1=O DYDCUQKUCUHJBH-UWTATZPHSA-N 0.000 description 3
- 229910017061 Fe Co Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/045—Electrochemical coating; Electrochemical impregnation
- H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
-
- 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
- H01M10/24—Alkaline accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
Abstract
The invention belongs to the field of electrochemical energy storage, and particularly relates to an antimony cathode and a water-based alkaline battery based on the antimony cathode. The invention discloses an antimony negative electrode, which comprises a substrate and antimony metal deposited on the substrate; antimony metal is electrodeposited onto the substrate using a solution of alkali and antimony source as an electrolyte. The antimony negative electrode prepared by the method has the characteristics of lower electrode potential, high specific capacity, excellent rate performance, good cycling stability, low cost, environmental friendliness and the like. The aqueous alkaline battery of the invention based on an antimony negative electrode has a high energy density and a long cycle life.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to an antimony negative electrode and an aqueous alkaline battery based on the antimony negative electrode.
Background
The aqueous alkaline battery takes an alkaline aqueous solution as an electrolyte, is an important electrochemical power system, and has the advantages of high energy density, high power density, low cost, high safety, simple preparation process, cleanness, no pollution and the like. The method is applied to the fields of small-sized electric appliances, portable electronic products, electric vehicles, power grid energy storage and the like. Most of the research is mainly focused on the anode material at present, and practical progress is made. However, the performance of the currently developed negative electrode material is far behind that of the positive electrode, and the application and development of the water-based alkaline battery are severely restricted. For example, the nickel-zinc, nickel-iron and nickel-cadmium batteries widely reported at present all face the problems of low energy density, poor cycle life and the like, and cannot meet the requirements of future portable, light and miniature devices.
The development of aqueous alkaline batteries has been long, however, the development of the system in practical application is seriously influenced by the hysteresis of the negative electrode material, and the system is also a main challenge to the development. Negative electrode materials in aqueous alkaline batteries can be classified into two types, one being a conversion type negative electrode and the other being a deposition/dissolution type negative electrode, according to the energy storage mechanism. The former mainly stores energy through oxidation-reduction reaction generated in the charging and discharging process, such as bismuth, cadmium, iron oxide and other materials. The latter, in turn, typically stores and releases energy through the process of deposition/dissolution of the metal on the electrode surface. Deposition/dissolution type anodes (e.g., zinc anodes) have faster reaction kinetics and higher charge transfer capabilities than conversion anodes. However, the deposition/dissolution type cathodes face severe dendrite problems as well as surface passivation/corrosion and hydrogen evolution side reactions. Thereby, a low energy density and stability result. Therefore, development of a novel deposition/dissolution type negative electrode material has injected new vigor into the development of aqueous alkaline batteries.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides the antimony negative electrode which has the characteristics of lower electrode potential, high specific capacity, excellent rate capability, good cycling stability, low cost, environmental friendliness and the like.
The invention also provides a preparation method of the antimony negative electrode.
The invention also provides an application of the antimony negative electrode in an alkaline battery.
The invention also provides an alkaline battery with the antimony negative electrode.
According to one aspect of the present invention, there is provided an antimony negative electrode comprising a substrate and antimony metal deposited on the substrate; and electrodepositing the antimony metal on the substrate by taking a mixed solution of alkali and an antimony source as an electrolyte.
In some embodiments of the invention, the substrate is a carbon material or a metal, i.e., a carbon material or a metal is the negative electrode current collector.
In some preferred embodiments of the present invention, the carbon material includes, but is not limited to, one or more of carbon fiber, porous carbon, carbon nanotubes, and acetylene black. The conductivity, wetting property, specific surface area and chemical adsorption property of the carbon material are main factors influencing the performance of the negative electrode of the antimony, and the high-quality carbon material substrate is beneficial to reversible deposition/dissolution of antimony metal on the surface of the antimony metal substrate and is beneficial to obtaining a water-based alkaline battery with high specific energy and long service life. The carbon material has rich selection types and low cost, and can meet the requirement of a low-cost power supply.
In some preferred embodiments of the present invention, the metal includes, but is not limited to, one or more of nickel, titanium, copper, lead, tin, bismuth, tin-antimony alloys, lead-antimony alloys, and copper-antimony alloys. The metal substrate has good conductivity and antimony affinity, so that the metal substrate can improve the deposition and dissolution processes of the antimony negative electrode, thereby improving the coulombic efficiency and the discharge depth of the antimony negative electrode and improving the specific capacity of the antimony negative electrode.
In some embodiments of the present invention, the electrolyte is an aqueous solution, i.e., the electrolyte is a mixed aqueous solution of alkali and antimony source.
In some embodiments of the invention, the base includes, but is not limited to, one or more of potassium hydroxide, sodium hydroxide, and lithium hydroxide.
In some preferred embodiments of the present invention, the concentration of the base in the mixed solution is 1 to 12 mol/L; for example, it may be 1mol/L, 2mol/L, 4mol/L, 6mol/L, 8mol/L, 10mol/L or 12 mol/L. The source of alkali is rich and the price is low, so that the application cost of the antimony cathode is reduced; the ionic conductivity of the electrolyte can be improved by regulating and controlling the alkali concentration, so that the charge-discharge reversibility and the cycle stability of the antimony cathode are regulated and controlled.
In some embodiments of the invention, the antimony source is a trivalent antimony source, in particularAnd may be a trivalent antimony salt. More specifically, the antimony source includes, but is not limited to, one or more of antimony acetate, antimony sulfate, antimony trichloride, and potassium antimony tartrate. The trivalent antimony source is dissolved in an alkaline electrolyte, in which antimony is present as SbO2 -May deposit on the substrate during charging to form the Sb metal. Different antimony sources have different coordination forms in alkali liquor, and show different states in desolvation process and surface adsorption, nucleation and growth process under the influence of different anions.
In some preferred embodiments of the present invention, the concentration of the antimony source in the mixed solution is 0.1 to 3 mol/L; for example, it may be 0.1mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, or 3 mol/L. By regulating the concentration of the antimony source, the deposition/solvent rate of antimony metal on the surface can be regulated, so that the rate performance of the antimony cathode can be regulated.
In some embodiments of the invention, the amount of antimony metal deposited is 0.5-10mAh cm-2For example, it may be 0.5mAh cm-2、2mAh cm-2、5mAh cm-2、7mAh cm-2Or 10mAh cm-2。
In some embodiments of the invention, the electrolyte further comprises an additive.
In some preferred embodiments of the invention, the concentration of the additive is 3mol/L or less, for example, 0.1mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, or 3 mol/L.
In some embodiments of the invention, the additive comprises a macrocationic salt and/or an anionic surfactant.
In some embodiments of the invention, the large cation salt includes, but is not limited to, one or more of Li, Na, Al, and Rb salts. In some embodiments of the invention, anionic surfactants include, but are not limited to, one or more of fatty acid salts, sulfonic acid salts, sulfuric acid ester salts, and phosphoric acid ester salts, such as sodium dodecyl sulfate, cetyltrimethylammonium bromide (CTAB), and/or sodium dodecyl sulfate, among others.
Adding large-size anode into electrolyteIons are beneficial to regulating and controlling the transfer rate of water molecules in the electrolyte, so that the deposition of antimony on the surface of the electrode is regulated and controlled. And the addition of the anionic surfactant is favorable for changing SbO2 -The coordination environment of ions and the reduction of SbO2 -The diffusion of ions on the surface of the electrode inhibits side reaction and regulates and controls the deposition morphology.
According to another aspect of the invention, the preparation method of the antimony negative electrode is provided, wherein a mixed solution of alkali and an antimony source is used as an electrolyte, and the antimony negative electrode is obtained through electrodeposition.
According to another aspect of the invention, the application of the antimony negative electrode in an alkaline battery is provided.
According to yet another aspect of the present invention, there is provided an alkaline battery comprising the above antimony negative electrode. Preferably, the alkaline battery is an aqueous alkaline battery.
The aqueous alkaline battery based on an antimony negative electrode according to the present invention focuses on the use of antimony as an active material of the negative electrode.
The invention adopts antimony element as the main cathode active material of the water system alkaline battery, and the working principle and the characteristics are as follows:
1) in alkaline electrolyte, metal Sb and SbO2 -The redox electrode potential between the two electrodes can reach about-0.66V vs. SHE, and the electrode potential is lower when the redox electrode is used as a negative electrode.
2) The antimony negative electrode has 660mAh g-1The high theoretical specific capacity and the low cost of about 7 $/kg.
3) In alkaline solution, antimony is present in the form of SbO2 -Sb and SbO2 -The energy storage and release can be carried out through a deposition/dissolution electrochemical reaction mechanism, and the electrochemical dynamic is excellent and is beneficial to the high-rate performance of the battery.
Therefore, the aqueous alkaline battery based on the antimony negative electrode has the characteristics of high specific capacity, high rate performance, long service life and the like.
The invention has the following beneficial effects:
the invention takes solution of alkali and antimony source as electricityAnd (4) electrolyte, and preparing the antimony negative electrode by an electrodeposition method. In alkaline solution, antimony is present in the form of SbO2 -Sb and SbO2 -Energy storage and release may occur through the electrochemical reaction mechanism of deposition/dissolution. The antimony negative electrode prepared by the method has the characteristics of lower electrode potential, high specific capacity, excellent rate performance, good cycling stability, low cost, environmental friendliness and the like. The aqueous alkaline battery of the invention based on an antimony negative electrode has a high energy density and a long cycle life.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 Scanning Electron Microscope (SEM) images of carbon fibers (CC) and carbon nanotube networks (CC-CNT) at different magnifications. Wherein, (a, b) CC; (c, d) CC-CNT.
FIG. 2 is a graph of Sb/CC and Sb/CC-CNT negative electrode performance. Wherein, (a) the cyclic voltammetry curve of the Sb/CC cathode; (b) cyclic voltammetry of the Sb/CC-CNT negative electrode; (c) Sb/CC and Sb/CC-CNT negative electrodes at the same current density (2mA cm)-2) Deposition/dissolution electrical curves at different capacities.
Figure 3 is an SEM image of the brass surface with antimony metal deposited at different magnifications.
FIG. 4 is a graph of the charge and discharge curves and the coulombic efficiency of an antimony negative electrode based on brass (2mA cm)-2，2mAh cm-2)。
FIG. 5 Effect of different concentrations of alkali on the charge and discharge behavior of antimony negative electrode (5mA cm)-2，0.5mAh cm-2)。
FIG. 6 the effect of different concentrations of antimony potassium tartrate on the performance of antimony negative electrodes; wherein (a) cyclic voltammogram (10mV s)-1) (ii) a (b) Charge and discharge curve (5mA cm)-2,0.5mAh cm-2)。
FIG. 7 Effect of different additives on the Charge-discharge Performance of antimony negative electrode (5mA cm)-2，0.5mAh cm-2)。
FIG. 8 CS and D-CS based Fe-Co (OH)2Performance plots of/Sb alkaline cells; wherein, (a) a charge-discharge curve; (b) multiplying power performance; (c) stable circulationAnd (5) performing qualitative determination.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise indicated, reagents and materials used in the present invention are commercially available. The concentration in this section is expressed as M (mol/L).
Example 1
Carbon fibers (CC) and carbon nanotube networks (CC-CNT) grown in situ on the carbon fibers are respectively used as substrates, a mixed solution of 3M KOH and 0.1M potassium antimony tartrate is used as an electrolyte, a graphite rod is used as a counter electrode, an Hg/HgO electrode is used as a reference electrode, the deposition capacity of Sb metal is fixed, and the deposition/dissolution performances of the Sb metal on the surfaces of different samples are respectively compared.
FIG. 1 is an SEM image of CC and CC-CNT. The carbon fiber has smooth surface and small specific surface area, and the carbon nanotube network is densely distributed on the carbon fiber to form a conductive network, so that the specific surface area is large, uniform holes are formed in gaps, and the storage and reaction of electrolyte are facilitated.
As shown in fig. 2, the Cyclic Voltammetry (CV) curves for the Sb/CC and Sb/CC-CNT anodes both exhibited a pair of symmetric redox peaks, corresponding to the deposition and dissolution of Sb metal. It can be seen that the Sb/CC-CNT negative electrode has greater current density and less polarization, indicating that the Sb/CC-CNT negative electrode has better conductivity and more reversible Sb metal deposition/dissolution. Furthermore, at 2mA cm -2Under the current density, CP curves with different capacities show that the Sb/CC-CNT negative electrode has excellent charge and discharge performance, higher coulombic efficiency, stronger hydrogen evolution inhibition effect and longer cycle life compared with the Sb/CC negative electrode.
Example 2
The cycle stability of the antimony negative electrode was tested by using brass as a substrate, a mixed solution of 3M KOH and 0.1M potassium antimony tartrate as an electrolyte, a graphite rod as a counter electrode, and an Hg/HgO electrode as a reference electrode, and depositing/dissolving Sb metal at constant current.
Fig. 3 is an SEM image of brass surface with antimony metal deposited. It can be seen that antimony metal can be uniformly deposited on the brass surface, the brass substrate is completely covered, and the deposited antimony metal particles are uniform in size and do not significantly bulge or fall off. The brass substrate and the antimony metal have good interaction, and the material is an excellent antimony negative electrode substrate material.
FIG. 4 is a graph of the charge-discharge curve and the coulombic efficiency of an antimony negative electrode based on brass at 2mA cm-2Current density, Sb deposition capacity 2mAh cm-2The antimony negative electrode can be stably cycled for 500 circles, and the coulombic efficiency of the antimony negative electrode can be kept above 80% at 400 circles, which shows that the brass substrate has good antimony metal reversible deposition/solubility.
Example 3
The charge and discharge performance of the antimony negative electrode was tested by using carbon fibers as a substrate, using mixed solutions of KOH and 0.1M of antimony potassium tartrate with different concentrations (1M, 2M, 3M, 4M and 6M) as electrolytes, using a graphite rod as a counter electrode, and using an Hg/HgO electrode as a reference electrode, respectively. Wherein the charge-discharge current density of the electrode is 5mA cm-2The deposition amount of antimony metal was 0.5mAh cm-2。
As can be seen from fig. 5, the concentration of KOH has a great influence on the charge and discharge performance of the antimony negative electrode, which has the smallest charge plateau when the concentration of KOH is 6M, and the highest coulombic efficiency and the smallest polarization when the concentration is 4M.
Example 4
Respectively testing the charge and discharge performance of an antimony negative electrode by taking carbon fiber as a substrate, 3M KOH and antimony potassium tartrate mixed solution with different concentrations (0.5M, 1M, 1.5M, 2M, 2.5M and 3M) as electrolyte, a graphite rod as a counter electrode and an Hg/HgO electrode as a reference electrode, wherein the charge and discharge current of the electrode is 5mA cm-2Antimony (II)The deposition amount of the metal was 0.5mAh cm-2。
It can be seen from fig. 6 that the cyclic voltammograms of the antimony negative electrodes show different polarization characteristics when different concentrations of antimony potassium tartrate are added, and the concentration of antimony potassium tartrate has a great influence on the current density. In addition, from the charge-discharge curve of the antimony negative electrode, it can be found that the charge-discharge plateau of the antimony negative electrode is greatly affected by the concentration of antimony potassium tartrate.
Example 5
The method comprises the steps of taking carbon fiber as a substrate, taking a mixed solution of 3M KOH and 0.1M potassium antimony tartrate as an electrolyte, simultaneously adding different additives (0.1M-1M) to modify the electrolyte, taking a graphite rod as a counter electrode, taking an Hg/HgO electrode as a reference electrode, and testing the charge and discharge performance of an antimony negative electrode, wherein the charge and discharge current of the electrode is 5mA cm-2The deposition amount of antimony metal was 0.5mAh cm-2。
It can be seen from fig. 7 that the electrolyte is modified by adding different surfactants, so that the deposition/dissolution efficiency of the antimony negative electrode can be improved well, and the coulomb efficiency of the antimony negative electrode can be improved.
Example 6
Respectively adopting carbon fiber (CS) and carbon fiber (D-CS) with abundant intrinsic carbon defects as substrates, a mixed solution of 3M KOH +0.1M potassium antimony tartrate as an electrolyte, and Fe-doped Co (OH)2(Fe-Co(OH)2) Assembled as a matching positive electrode of Fe-Co (OH)2// Sb alkaline cell.
As can be seen from FIG. 8, at a current density of 6mA cm-2Next, the Sb/D-CS electrode exhibited 0.32mAh cm-2And exhibits better rate performance; there was substantially no attenuation in area capacity and coulombic efficiency after 1800 cycles of charge and discharge cycles.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. An antimony negative electrode comprising a substrate and antimony metal deposited on the substrate; and electrodepositing the antimony metal on the substrate by taking a mixed solution of alkali and an antimony source as an electrolyte.
2. The antimony negative electrode of claim 1, wherein the substrate is a carbon material or a metal.
3. The antimony anode of claim 2, wherein the carbon material is selected from one or more of carbon fiber, porous carbon, carbon nanotubes, and acetylene black; the metal is selected from one or more of nickel, titanium, copper, lead, tin, bismuth, tin-antimony alloy, lead-antimony alloy and copper-antimony alloy.
4. The antimony negative electrode of claim 1, wherein the base is selected from one or more of potassium hydroxide, sodium hydroxide, and lithium hydroxide; the antimony source is a trivalent antimony source; the antimony source is one or more selected from antimony acetate, antimony sulfate, antimony trichloride and antimony potassium tartrate.
5. The antimony negative electrode according to claim 1, wherein the concentration of the alkali in the mixed solution is 1 to 12 mol/L; the concentration of the antimony source in the mixed solution is 0.1-3 mol/L; the deposition amount of the antimony metal is 0.5-10mAh cm -2。
6. The antimony negative electrode according to any one of claims 1-5, wherein the electrolyte further comprises an additive; the concentration of the additive is less than 3 mol/L.
7. The antimony negative electrode according to claim 6, wherein the additive comprises a macrocationic salt and/or an anionic surfactant; the large cation salt is selected from one or more of Li, Na, Al and Rb salts; the anionic surfactant is selected from one or more of fatty acid salt, sulfonate, sulfate ester salt and phosphate ester salt.
8. The method of producing an antimony negative electrode according to any one of claims 1 to 7, wherein the antimony negative electrode is obtained by electrodeposition using a mixed solution of alkali and an antimony source as an electrolyte.
9. Use of an antimony negative electrode as claimed in any one of claims 1 to 7 in an alkaline cell.
10. An alkaline battery comprising an antimony negative electrode according to any one of claims 1 to 7.
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| CN108199003A (en) * | 2017-12-27 | 2018-06-22 | 长安大学 | A kind of big/mesoporous antimony cathode of three-dimensional, preparation method and applications |
| CN110350146A (en) * | 2019-06-03 | 2019-10-18 | 长安大学 | A kind of porous antimony electrode of modified 3 D, preparation method and application |
| CN111916720A (en) * | 2020-07-30 | 2020-11-10 | 山东大学 | Alloy type negative electrode material of water system rechargeable zinc ion battery and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108199003A (en) * | 2017-12-27 | 2018-06-22 | 长安大学 | A kind of big/mesoporous antimony cathode of three-dimensional, preparation method and applications |
| CN110350146A (en) * | 2019-06-03 | 2019-10-18 | 长安大学 | A kind of porous antimony electrode of modified 3 D, preparation method and application |
| CN111916720A (en) * | 2020-07-30 | 2020-11-10 | 山东大学 | Alloy type negative electrode material of water system rechargeable zinc ion battery and preparation method and application thereof |
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