CN117317194A - Bi-M double-doped birnessite material, preparation method thereof and application thereof in zinc ion battery - Google Patents
Bi-M double-doped birnessite material, preparation method thereof and application thereof in zinc ion battery Download PDFInfo
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- CN117317194A CN117317194A CN202311486879.0A CN202311486879A CN117317194A CN 117317194 A CN117317194 A CN 117317194A CN 202311486879 A CN202311486879 A CN 202311486879A CN 117317194 A CN117317194 A CN 117317194A
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- 239000000463 material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims description 23
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 22
- 239000011572 manganese Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 238000004729 solvothermal method Methods 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- 239000007774 positive electrode material Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 13
- 235000002639 sodium chloride Nutrition 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- -1 organic acid salt Chemical class 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 229910013643 M-Sn Inorganic materials 0.000 abstract 1
- 229910013672 M—Sn Inorganic materials 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000010405 anode material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 229910016338 Bi—Sn Inorganic materials 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 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 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
-
- 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 belongs to the field of battery materials, and particularly discloses a preparation method of a Bi-M double-doped birnessite material, which comprises the steps of carrying out a first-stage solvothermal reaction on a Bi source, an M metal source and chloride, and carrying out solid-liquid separation to obtain M-BiOCl, wherein M is at least one of Sn, ni and Fe; and carrying out a second-stage solvothermal reaction on the M-BiOCl, the permanganate source and the divalent manganese source to obtain the Bi-M double-doped birnessite material. The invention also comprises the Bi-M double-doped birnessite material prepared by the preparation method and application thereof. The preparation method disclosed by the invention can successfully realize double doping of M-Sn and improve the performance of the prepared material.
Description
Technical Field
The invention belongs to the field of batteries, and particularly relates to the technical field of water-based zinc ion battery anode materials.
Background
With the rapid development of portable electronic devices and new energy automobiles, the demand for rechargeable batteries is also increasing. Zinc Ion Batteries (ZIBs) have attracted considerable attention from researchers because zinc has the advantages of being naturally abundant, low-cost, environmentally friendly, and the like. In recent years, materials such as manganese-based oxides, vanadium-based oxides, prussian blue, and the like have been developed as cathode materials for aqueous zinc ion batteries. Among them, manganese-based oxides are considered as one of the most promising cathode materials due to their natural abundance, low cost, and low toxicity. Further applications are limited due to their low conductivity and structural instability. Thus, developing manganese-based oxide materials with high specific capacities and long cycle lives presents a significant challenge. In order to solve the above-described problems of manganese-based oxides, metal element doping is considered to be the most effective method. However, the manganese-based oxide can not absolutely inhibit the dissolution of manganese by replacing the manganese site with a single metal ion, so that satisfactory cycle performance is obtained. In recent years, significant progress is made in improving the electrochemical performance of manganese-based oxides by utilizing a metal element co-doping strategy, so that Jahn-Teller distortion is effectively inhibited, and the circulation stability is improved.
For example, patent publication No. CA2964761C discloses a mixed material cathode for a secondary alkaline battery, which battery includes a mixed cathode material having birnessite phase manganese dioxide or Electrolytic Manganese Dioxide (EMD), a bismuth compound, and a copper compound selected from elemental copper and copper salts. Patent document publication No. WO2023071354A1 discloses a method for preparing a doped manganese-based sodium ion battery positive electrode material, comprising: dissolving one or two of antimony trioxide and bismuth trioxide by acid, adding divalent manganese salt to prepare mixed metal salt solution, adding the mixed metal salt solution into alkaline oxidant solution to react, carrying out solid-liquid separation to obtain solid materials, drying the solid materials, mixing the solid materials with a sodium source, and sintering to obtain the doped manganese-based sodium ion battery anode material.
Although the prior art reports some ways of metal doping, there are fewer Bi-M, especially Bi-Sn Bi-metal hybridization schemes.
Disclosure of Invention
Aiming at the technical blank of the existing Bi-M double-doped birnessite material and the difficult preparation problem of Bi-M double doping, the first aim of the invention is to provide a preparation method of the Bi-M double-doped birnessite material (also called Bi-M double-doped birnessite manganese dioxide material) and aims at solving the problem of difficult double doping of Bi-M.
The second purpose of the invention is to provide the Bi-M double-doped birnessite material prepared by the preparation method and the application of the Bi-M double-doped birnessite material in a water-based zinc ion battery.
The third object of the present invention is to provide an aqueous zinc ion battery comprising the Bi-M double doped birnessite material, and a positive electrode material thereof.
Bi-M double ions are difficult to successfully double dope birnessite, the type of material still belongs to the technical blank, and aiming at the problem, the invention provides the following improvement scheme through intensive research:
a preparation method of Bi-M double-doped birnessite material comprises the following steps:
step (1):
carrying out first-stage solvothermal reaction on a Bi source, an M metal source and chloride, and carrying out solid-liquid separation to obtain M-BiOCl, wherein M is at least one of Sn, ni and Fe;
step (2):
and carrying out a second-stage solvothermal reaction on the M-BiOCl, the permanganate source and the divalent manganese source to obtain the Bi-M double-doped birnessite material.
Aiming at the problem that Bi-M is difficult to successfully dope birnessite, the invention innovatively carries out a first section of solvothermal reaction on a Bi source, an M metal source and a chloride in advance, and then carries out a second section of solvothermal reaction on the Bi source, the M metal source and a divalent manganese source, so that the synergy can be realized unexpectedly, the doping of Bi-M bimetallic ions of birnessite can be successfully realized, and the chemical properties of the prepared material can be improved.
In the invention, the combination of the Bi source, the M metal source and the chloride for the first-stage solvothermal reaction and the second-stage solvothermal reaction with the subsequent permanganate source and the divalent manganese source is a key for realizing synergy, successfully preparing the Bi-M double-doped birnessite material and improving the electrochemical performance of the prepared material.
In the invention, the Bi source and the M metal source are water-soluble salts of respective metals, preferably at least one of nitrate, hydrochloride, organic acid salt and sulfate;
in the invention, M is Sn;
in the present invention, the chloride may be any compound capable of providing Cl, and may be at least one of sodium chloride, potassium chloride, ammonium chloride, stannous chloride, nickel chloride and ferrous chloride;
in the invention, the molar ratio of Bi, M and Cl elements in Bi source, M metal source and chloride is 1:0.04 to 0.10:1 to 2.2; further preferably 1:0.04 to 0.08:1.5 to 2.1.
The solvent of the first section of solvothermal is at least one of water and organic solvent; the organic solvent is a solvent which can be mixed with water;
preferably, the concentration of solute in the first-stage solvothermal starting solution is 0.05-0.08M;
preferably, the temperature of the first stage solvothermal is 130-200 ℃, preferably 150-180 ℃;
preferably, the time of the first stage solvothermal is 14-18 h.
In the invention, the permanganate source is potassium permanganate;
preferably, the divalent manganese source is a water soluble salt of divalent manganese;
preferably, the molar ratio of the permanganate source to the divalent manganese source is 5-10: 1, more preferably 6 to 8:1;
preferably, the weight ratio of the M-BiOCl to the permanganate source is 0.1-0.4: 1, preferably 0.2 to 0.3:1, and more preferably 0.22 to 0.28:1. Research has shown that the double doping effect can be unexpectedly further improved at the preferred ratio, and the electrochemical properties of the prepared material can be further improved.
In the invention, the solvent of the second solvent heat is at least one of water and organic solvent; the organic solvent is a solvent which can be mixed with water;
preferably, the concentration of permanganate in the second-stage solvothermal starting solution is between 0.05 and 0.12M;
preferably, the temperature of the second stage solvothermal is 130-200 ℃, preferably 160-190 ℃;
preferably, the second stage solvothermal time is from 10 to 16 hours, preferably from 11 to 14 hours.
The invention also provides the Bi-M double-doped birnessite material prepared by the preparation method.
The research of the invention shows that the preparation method can endow the material with special physical and chemical characteristics, and the material with the characteristics prepared by the preparation method can unexpectedly show excellent electrochemical performance.
The invention also provides an application of the Bi-M double-doped birnessite material prepared by the preparation method, and the Bi-M double-doped birnessite material is used as a positive electrode active material for preparing a water-based zinc ion battery.
In the invention, the Bi-M double-doped birnessite material can be used as an anode active material, and can be singly or jointly used with other conventional anode active materials to prepare a required water-based zinc ion battery and an anode material thereof based on conventional principles and modes.
The invention also provides a positive electrode material of the water-based zinc ion battery, which comprises a positive electrode active material, a binder and a conductive agent, wherein the positive electrode active material comprises the Bi-M double-doped birnessite material prepared by the preparation method;
in the positive electrode active material of the present invention, the content of the Bi-M double-doped birnessite material may be adjusted as required, for example, may be 50wt.% or more, and further may be 90wt.% or more;
in the present invention, the binder and the conductive agent may be conventional.
In the positive electrode material of the present invention, the content of the positive electrode active material is not particularly limited, and may be, for example, 50wt.% or more, preferably 70 to 90wt.%.
The invention also provides a positive electrode of the water-based zinc ion battery, which comprises a current collector and a positive electrode material compounded on the surface of the current collector, wherein the positive electrode material is the positive electrode material;
in the present invention, the current collector may be conventional in the industry, and may be, for example, a titanium foil.
The invention also provides a water-based zinc ion battery, which comprises a battery core of a positive electrode, a diaphragm and a negative electrode which are mutually compounded, and electrolyte for soaking the battery core, wherein the positive electrode is the positive electrode of the invention;
in the invention, other components and parts of the zinc ion battery can be conventional except for the Bi-M double-doped birnessite material prepared by the preparation method.
For example, the negative electrode is zinc foil or a negative electrode loaded with zinc metal;
for example, the electrolyte is an aqueous solution in which zinc ion salts are dissolved.
Advantageous effects
Aiming at the problem that Bi-M is difficult to successfully dope birnessite, the invention innovatively carries out a first section of solvothermal reaction on a Bi source, an M metal source and a chloride in advance, and then carries out a second section of solvothermal reaction on a permanganate source and a divalent manganese source, so that the synergy can be realized unexpectedly, the doping of Bi-M bimetallic ions of birnessite can be successfully realized, and the chemical properties of the prepared material can be improved.
The Bi-M double-doped birnessite material prepared by the invention shows extremely high specific capacity, stable cycle performance and rate capability when being applied to a water-based zinc ion battery anode material, and the performance reported by the similar materials at present is dominant.
Drawings
FIG. 1 is an XRD pattern of Bi-Sn-birnessite obtained in example 1.
FIG. 2 is an SEM image of Bi-Sn-birnessite obtained in example 1.
Fig. 3 is a graph showing charge-discharge cycle comparison of the positive electrode materials of the aqueous zinc-ion batteries of example 1, example 2 and example 3 at a current density of 100 mAh/g.
Fig. 4 is a graph showing charge-discharge cycle comparison of example 1, comparative example 2, comparative example 3, and comparative example 4 as positive electrode materials of aqueous zinc-ion batteries at a current density of 100 mAh/g.
Detailed Description
Aiming at the problems that the birnessite positive electrode material in the prior art is unstable in structure in the charge-discharge cycle process, the birnessite structure is easy to be destroyed and collapse to cause the attenuation of electrochemical performance and the like, the preparation method of the Bi-M (Bi) double-ion doped birnessite positive electrode material is provided. The method utilizes a hydrothermal method to dope Sn into birnessite 2+ And Bi (Bi) 3+ The double ions are used for adjusting the stability of the internal structure of the material, effectively inhibiting the dissolution of the birnessite, and simultaneously effectively improving the conductivity of the material, and finally obtaining the birnessite doped with the double ions. The material obtained by the invention is used as a positive electrode material to form a water-based zinc ion battery, and has excellent electrochemical performance.
As an embodiment of the preparation of Bi-M (e.g., bi) double ion doped birnessite in the present invention, there may be mentioned, for example, the following steps:
s1, preparing Sn-BiOCl: bismuth nitrate pentahydrate, sodium chloride and stannous chloride dihydrate are added into deionized water and stirred uniformly, the solution is subjected to hydrothermal reaction, the hydrothermal temperature is 130-200 ℃, and the hydrothermal time is 14-18 h.
S2, preparing Bi-Sn-birnessite: the preparation method of the solution A comprises the following steps: and adding the Sn-BiOCl into deionized water for uniform dispersion, and then adding the potassium permanganate for full and uniform stirring.
S3, the preparation method of the solution B comprises the following steps: adding manganese sulfate into deionized water, and stirring thoroughly and uniformly.
S4, adding the solution B into the solution A to obtain a solution C, and vigorously stirring the solution C at 15-30 ℃ to obtain a solution D.
S5, adding the solution D into a high-pressure reaction kettle to perform hydrothermal reaction. Wherein the temperature of the hydrothermal reaction is 130-200 ℃ and the hydrothermal time is 10-16 h.
S6, centrifugally collecting the product after the hydrothermal reaction is finished, washing with deionized water, and drying to obtain the product Bi-Sn-birnessite.
Further, the uniform dispersion in the preparation process of the solution A is ultrasonic dispersion, and the ultrasonic dispersion time is 15-30min.
Further, the concentration of the potassium permanganate is 0.01-0.1mol/L.
Further, the stirring is fully and uniformly carried out for 30-60 min.
Further, the concentration of the manganese sulfate is 0.001-0.01mol/L.
Further, the solution C is vigorously stirred at 15-30 ℃ for 30-60 min.
Example 1
(1) Preparation of Sn-BiOCl:
0.48g of bismuth nitrate pentahydrate (1 mmol), sodium chloride (1 mmol) and stannous chloride dihydrate (0.05 mmol) are added into 40ml of deionized water and stirred uniformly, and the solution is subjected to hydrothermal reaction at 160+/-5 ℃ for 16 hours.
(2) 0.1933gSn-BiOCl is added into 50mL of deionized water for ultrasonic dispersion for 0.5h, and then 0.79g of potassium permanganate (5 mmol) is added for vigorous stirring for 0.5h, so as to obtain solution A.
0.1g of manganese sulfate (0.66 mmol) was added to 10mL of deionized water and vigorously stirred for 0.5h, to give solution B.
And adding the solution B into the solution A to obtain a solution C, and vigorously stirring the solution C at 15-30 ℃ for 1h to obtain a solution D.
(3) And adding the solution D into a high-pressure reaction kettle to perform hydrothermal reaction. Wherein the temperature of the hydrothermal reaction is 180+/-5 ℃ and the hydrothermal time is 12 hours.
(4) And centrifugally collecting the product after the hydrothermal reaction is finished, washing the product with deionized water for 3 times, and drying the product at 80 ℃ for 12 hours to obtain the product Bi-Sn-birnessite (positive electrode active material).
XRD of the prepared material is shown in figure 1, SEM is shown in figure 2, and the Bi-Sn double ion doped birnessite material is successfully prepared.
And (3) carrying out battery assembly on the prepared positive electrode active material: the electrochemical performance of the positive electrode composite material is tested by adopting a 2030 button cell. The positive electrode active material, conductive carbon black and PVDF (polyvinylidene fluoride) prepared by the method are prepared according to the mass of 7:2:1 are uniformly dissolved in a nitrogen methyl pyrrolidone solution to prepare slurry, then the slurry is uniformly coated on the surface of a titanium foil (the thickness of the titanium foil is 0.02 mm), and the titanium foil is dried in an oven at 70 ℃ for 12 hours, and then the pole piece is cut to assemble the battery.
The battery assembling method comprises the following steps: the positive plate is used as a positive electrode, the metallic zinc is used as a negative electrode, and ZnSO is used as a negative electrode 4 And MnSO 4 The mixed aqueous solution is used as electrolyte, and ZnSO in the electrolyte 4 2M, mnSO 4 At 0.2M, glass fiber film was used for the separator.
And (3) battery testing: the assembled battery is tested by adopting a new Will high-performance battery testing system at the room temperature of 20-25 ℃ and 0.1Ag -1 And (5) testing the constant current charge and discharge.
Example 2
The difference compared with example 1 is that Sn-BiOCl is added in an amount of 0.29g.
Example 3
The difference compared with example 1 is that Sn-BiOCl is added in an amount of 0.116g.
Comparative example 1
The difference compared with example 1 is that step (1) is not performed, and in step 2, sn-BiOCl is not added to solution A, and the final product is birnessite.
Comparative example 2
The difference compared to example 1 is only that in step (1), the first stage solvothermal of step 1 is not performed, but instead, the Sn-BiOCl is taken as part of step 2 and subsequent steps with the raw materials of bismuth nitrate pentahydrate, sodium chloride, stannous chloride dihydrate, which are synthesized to the same weight of Sn-BiOCl.
Other operations and parameters were the same as in example 1. Research has shown that this method does not achieve good electrochemical performance.
Comparative example 3
The birnessite prepared in comparative example 1 and Sn-BiOCl prepared in step 1 of example 1 were physically mixed (the physical mixing ratio of birnessite and Sn-BiOCl is the same as in example 1), to obtain a positive electrode active material, and an electrochemical performance test was performed with reference to the method of example 1.
Comparative example 4
The difference compared with example 1 is that in step (1), stannous chloride dihydrate was not added, and BiOCl was prepared and the same amount of tin-BiOCl was replaced for the treatment of step 2 and the subsequent treatments.
The electrochemical data in each case are shown in fig. 4, and the material obtained by the process has excellent cycling stability.
Claims (10)
1. The preparation method of the Bi-M double-doped birnessite material is characterized by comprising the following steps of:
step (1):
carrying out first-stage solvothermal reaction on a Bi source, an M metal source and chloride, and carrying out solid-liquid separation to obtain M-BiOCl, wherein M is at least one of Sn, ni and Fe;
step (2):
and carrying out a second-stage solvothermal reaction on the M-BiOCl, the permanganate source and the divalent manganese source to obtain the Bi-M double-doped birnessite material.
2. The method for preparing Bi-M double doped birnessite material according to claim 1, wherein the Bi source and the M metal source are water soluble salts of respective metals, preferably at least one of nitrate, hydrochloride, organic acid salt and sulfate;
preferably, M is Sn;
preferably, the chloride is at least one of sodium chloride, potassium chloride, ammonium chloride, stannous chloride, nickel chloride and ferrous chloride;
preferably, the molar ratio of Bi, M and Cl elements in the Bi source, the M metal source and the chloride is 1:0.04 to 0.10:1 to 2.2.
3. The method for preparing Bi-M double doped birnessite material according to claim 1, wherein the solvent of the first solvent heat is at least one of water and organic solvent; the organic solvent is a solvent which can be mixed with water;
preferably, the concentration of solute in the first-stage solvothermal starting solution is 0.05-0.08M;
preferably, the temperature of the first stage solvothermal is 130-200 ℃, preferably 150-180 ℃;
preferably, the time of the first stage solvothermal is 14-18 h.
4. The method for preparing the Bi-M double-doped birnessite material according to claim 1, wherein the permanganate source is potassium permanganate;
preferably, the divalent manganese source is a water soluble salt of divalent manganese;
preferably, the molar ratio of the permanganate source to the divalent manganese source is 5-10: 1, a step of;
preferably, the weight ratio of the M-BiOCl to the permanganate source is 0.1-0.4: 1, preferably 0.2 to 0.3:1.
5. The method for preparing Bi-M double doped birnessite material according to claim 1, wherein the solvent of the second solvent heat is at least one of water and organic solvent; the organic solvent is a solvent which can be mixed with water;
preferably, the concentration of permanganate in the second-stage solvothermal starting solution is between 0.05 and 0.12M;
preferably, the temperature of the second stage solvothermal is 130-200 ℃, preferably 160-190 ℃;
preferably, the second stage solvothermal time is from 10 to 16 hours, preferably from 11 to 14 hours.
6. The Bi-M double doped birnessite material prepared by the preparation method of any one of claims 1 to 5.
7. The use of the Bi-M double doped birnessite material prepared by the preparation method of any one of claims 1 to 5 as a positive electrode active material for preparing a water-based zinc ion battery.
8. A positive electrode material of a water-based zinc ion battery, comprising a positive electrode active material, a binder and a conductive agent, wherein the positive electrode active material comprises the Bi-M double-doped birnessite material prepared by the preparation method of any one of claims 1 to 5;
preferably, in the positive electrode active material, the content of the Bi-M double-doped birnessite material is more than 50 wt%;
preferably, in the positive electrode material, the content of the positive electrode active material is 50wt.% or more, preferably 70 to 90wt.%.
9. A positive electrode of a water-based zinc ion battery, which comprises a current collector and a positive electrode material compounded on the surface of the current collector, and is characterized in that the positive electrode material is the positive electrode material of claim 8;
preferably, the current collector is a titanium foil.
10. An aqueous zinc ion battery, comprising a battery core of a positive electrode, a diaphragm and a negative electrode which are mutually compounded, and electrolyte for soaking the battery core, wherein the positive electrode is the positive electrode of claim 9;
preferably, the negative electrode is zinc foil or a negative electrode loaded with zinc metal;
preferably, the electrolyte is an aqueous solution in which zinc ion salts are dissolved.
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