CN118420006A - Multi-metal hydroxide nanosheets and preparation method and application thereof - Google Patents
Multi-metal hydroxide nanosheets and preparation method and application thereof Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 51
- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 69
- 239000002184 metal Substances 0.000 claims abstract description 69
- 150000003839 salts Chemical class 0.000 claims abstract description 66
- 229920005862 polyol Polymers 0.000 claims abstract description 35
- 150000003077 polyols Chemical class 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000003960 organic solvent Substances 0.000 claims abstract description 33
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 29
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 19
- 239000003446 ligand Substances 0.000 claims abstract description 15
- 150000001768 cations Chemical class 0.000 claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- 239000002064 nanoplatelet Substances 0.000 claims description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 229910052723 transition metal Inorganic materials 0.000 claims description 20
- 150000003624 transition metals Chemical class 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 150000002910 rare earth metals Chemical class 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 abstract description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 229910001220 stainless steel Inorganic materials 0.000 description 16
- 239000010935 stainless steel Substances 0.000 description 16
- 238000002484 cyclic voltammetry Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 229910021645 metal ion Inorganic materials 0.000 description 10
- 239000012265 solid product Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 8
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- 238000005406 washing Methods 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
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- 238000001035 drying Methods 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
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- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
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- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
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- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a multi-element metal hydroxide nano-sheet, a preparation method and application thereof, and relates to the technical field of new energy storage and conversion. The preparation method of the multi-element metal hydroxide nano sheet provided by the invention comprises the following steps: dissolving first metal salt in a polyol organic solvent to carry out coordination reaction to obtain a precursor; dispersing the precursor in a second metal salt aqueous solution, and performing hydrolysis reaction to obtain the multi-element metal hydroxide nano-sheet; the cations of the second metal salt in the second metal salt aqueous solution are different from the cations of the first metal salt; the polyol organic solvent comprises an organic solvent and a polyol ligand; the volume ratio of the organic solvent to the polyol ligand is 10:1-5:1. The multi-element metal hydroxide nano-sheet prepared by the invention has stable structure, is not easy to agglomerate, and has excellent specific capacitance/capacity and rate capability.
Description
Technical Field
The invention belongs to the technical field of new energy storage and conversion, and particularly relates to a multi-element metal hydroxide nano sheet and a preparation method and application thereof.
Background
The transition metal hydroxide has the properties of changeable phase structure, interlayer spacing, electronic structure, chemical bonding and the like due to the adjustability of the constituent elements and the controllability of the morphology structure, and has important application in the technical fields of energy conversion and storage (electrochemical oxygen evolution, hybrid super capacitor and the like), biological medicine (drug loading and slow release, tumor treatment), nano sensing, water treatment and the like. Among them, the hybrid supercapacitor and the alkaline zinc ion battery constructed by using the transition metal hydroxide as the battery type positive electrode material are receiving much attention.
In the prior art, the transition metal hydroxide is usually prepared by direct precipitation reaction of transition metal salt and an alkali source (such as urea, sodium hydroxide and the like), the preparation method easily causes aggregation of lamellar structures of the transition metal hydroxide, electrochemical reaction kinetics and active site exposure in the charge and discharge process are seriously influenced, and the defect of poor specific capacitance/capacity and rate capability exists.
Disclosure of Invention
The invention aims to provide a multi-element metal hydroxide nano sheet, a preparation method and application thereof.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
a method for preparing a multi-element metal hydroxide nano-sheet, which comprises the following steps:
dissolving first metal salt in a polyol organic solvent to carry out coordination reaction to obtain a precursor;
dispersing the precursor in a second metal salt aqueous solution, and performing hydrolysis reaction to obtain the multi-element metal hydroxide nano-sheet;
the cations of the second metal salt in the second metal salt aqueous solution are different from the cations of the first metal salt;
The polyol organic solvent comprises an organic solvent and a polyol ligand; the volume ratio of the organic solvent to the polyol ligand is 10:1-5:1.
Preferably, the first metal salt is one or more of nitrate, chloride and acetate of a transition metal; the transition metal includes one or more of nickel, cobalt, manganese, zinc, vanadium, molybdenum, and copper.
Preferably, the organic solvent comprises one or more of methanol, ethanol, isopropanol, N-dimethylformamide, acetone and N-methylpyrrolidone; the polyol ligand is polyol with functionality more than or equal to 3.
Preferably, the dosage ratio of the first metal salt to the polyol organic solvent is 14.55-698.4 mg:32-362 mL.
Preferably, the second metal salt in the second metal salt aqueous solution is one or more of nitrate, chloride and acetate of transition metal or rare earth metal; the transition metal comprises one or more of nickel, cobalt, manganese, zinc, vanadium, molybdenum and copper; the rare earth metal comprises lanthanum and/or cerium.
Preferably, the dosage ratio of the precursor to the second metal salt aqueous solution is 1:0.5-1:10 mg/mL; the concentration of the second metal salt in the second metal salt aqueous solution is 0.083-4.0 mg/mL.
Preferably, the temperature of the coordination reaction is 140-200 ℃ and the time is 4-12 h.
Preferably, the temperature of the hydrolysis reaction is 90-180 ℃ and the time is 2-10 h.
The invention also provides the multi-element metal hydroxide nano-sheet prepared by the preparation method.
The invention also provides application of the multi-element metal hydroxide nano sheet in a super capacitor or a zinc ion battery.
The invention provides a preparation method of a multi-element metal hydroxide nano sheet, which comprises the following steps: dissolving first metal salt in a polyol organic solvent to carry out coordination reaction to obtain a precursor; dispersing the precursor in a second metal salt aqueous solution, and performing hydrolysis reaction to obtain the multi-element metal hydroxide nano-sheet; the cations of the second metal salt in the second metal salt aqueous solution are different from the cations of the first metal salt; the polyol organic solvent comprises an organic solvent and a polyol ligand; the volume ratio of the organic solvent to the polyol ligand is 10:1-5:1. The self viscosity of the polyalcohol organic solvent in the reaction process can slow down the formation rate of the precursor, so that the precursor grows more uniformly; meanwhile, the precursor is induced to be converted into the multi-element metal hydroxide nano-sheet by matching with second metal salt in second metal salt aqueous solution, on one hand, the intrinsic conductivity of the hydroxide nano-sheet is synergistically adjusted by introducing multi-element metal ions, and the electron transfer in the electrochemical reaction process is promoted; on the other hand, the electrochemical active area of the hydroxide nano-sheet can be increased, the contact between electrolyte ions and reactive sites can be increased, and the specific capacitance/capacity of the hydroxide nano-sheet can be further improved; meanwhile, the multi-element metal hydroxide nano-sheet prepared by the induction of the second metal salt in the second metal salt aqueous solution can effectively relieve the problems of stacking and agglomeration of sheets, greatly expose more reactive sites, further promote the oxidation-reduction reaction between the hydroxide nano-sheet and electrolyte ions, and further improve the specific capacitance/capacity of the hydroxide nano-sheet.
Meanwhile, the invention can rapidly realize the element composition in the target product multi-element metal hydroxide nano-sheet by regulating and controlling the difference between the cations of the second metal salt and the cations of the first metal salt in the second metal salt aqueous solution, even can introduce additional vacancy defect sites, and the vacancy defect can not only effectively regulate and control the electronic structure of the hydroxide nano-sheet and the adsorption capacity of electrolyte ions, but also etch the unsaturated coordination environment of the hydroxide nano-sheet into another electrochemical active center, thereby further improving the specific capacitance/capacity and rate capability of the multi-element metal hydroxide nano-sheet.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM photograph of NiCoMnZn-OH nanoplatelets prepared in example 2;
FIG. 2 is an AFM photograph of NiCoMnZn-OH nanoplatelets prepared in example 2;
FIG. 3 is an XRD spectrum of NiCoMnZn-OH nanoplatelets prepared in example 2;
FIG. 4 is a Cyclic Voltammogram (CV) test result of the NiCoZn-OH nanoplatelets prepared in example 1;
FIG. 5 is a constant current charge-discharge curve (GCD) test result of NiCoZn-OH nanoplatelets prepared in example 1;
FIG. 6 is a Cyclic Voltammogram (CV) test result of NiCoMnZn-OH nanoplatelets prepared in example 2;
FIG. 7 is a constant current charge-discharge curve (GCD) test result of NiCoMnZn-OH nanoplatelets prepared in example 2;
FIG. 8 is a Cyclic Voltammogram (CV) test result of NiCoMnCe-OH nanoplatelets prepared in example 3;
FIG. 9 is a constant current charge-discharge curve (GCD) test result of NiCoMnCe-OH nanoplatelets prepared in example 3.
Detailed Description
The invention provides a preparation method of a multi-element metal hydroxide nano sheet, which comprises the following steps:
dissolving first metal salt in a polyol organic solvent to carry out coordination reaction to obtain a precursor;
dispersing the precursor in a second metal salt aqueous solution, and performing hydrolysis reaction to obtain the multi-element metal hydroxide nano-sheet;
the cations of the second metal salt in the second metal salt aqueous solution are different from the cations of the first metal salt;
The polyol organic solvent comprises an organic solvent and a polyol ligand; the volume ratio of the organic solvent to the polyol ligand is 10:1-5:1.
In the present invention, all the preparation materials are preferably commercially available products well known to those skilled in the art unless specified otherwise.
The method comprises the steps of dissolving first metal salt in a polyol organic solvent to carry out coordination reaction to obtain a precursor. In the present invention, the first metal salt is preferably one or more of nitrate, chloride and acetate of a transition metal, more preferably nitrate of a transition metal. In the present invention, the transition metal preferably includes one or more of nickel, cobalt, manganese, zinc, vanadium, molybdenum, and copper, more preferably cobalt and nickel, or more preferably cobalt, nickel, and manganese. In an embodiment of the present invention, when the first metal salt is preferably Ni (NO 3)2·6H2 O and Co (NO 3)2·6H2 O), the mass ratio of Ni (NO 3)2·6H2 O to Co (NO 3)2·6H2 O) is preferably 14.5 to 174.6:0 to 116.4, more preferably 43.6 to 87.3:43.4 to 101.8, and when the first metal salt is preferably Ni (NO 3)2·6H2O、Co(NO3)2·6H2 O and Mn (NO 3)2·4H2 O), the mass ratio of Ni (NO 3)2·6H2O、Co(NO3)2·6H2 O to Mn (NO 3)2·4H2 O) is preferably 14.5 to 174.6:0 to 116.4:0 to 100.5, more preferably 87.3:58.2:25.1).
In the present invention, the polyol organic solvent includes an organic solvent and a polyol ligand. In the present invention, the organic solvent preferably includes one or more of methanol, ethanol, isopropanol, N-dimethylformamide, acetone and N-methylpyrrolidone, more preferably isopropanol. In the present invention, the polyol ligand is preferably a polyol having a functionality of 3 or more, more preferably one or more of glycerol, diglycerol, pentaerythritol and pentanol, and still more preferably glycerol. In the invention, the volume ratio of the organic solvent to the polyol ligand is preferably 10:1-5:1, more preferably 9:1-8:1. In the invention, the self-viscosity of the polyol organic solvent in the reaction process can slow down the formation rate of the precursor, so that the precursor can grow more uniformly, and the aggregation of the lamellar structure of the transition metal hydroxide is prevented.
In the invention, the dosage ratio of the first metal salt to the polyol organic solvent is preferably 14.55-698.4 mg:32-362 mL, more preferably 130.7-170.6 mg:70-85 mL.
The present invention dissolves a first metal salt in a polyol organic solvent. In the present invention, the temperature of the dissolution is preferably room temperature, more preferably 26 ℃; the time is preferably 8-10 min; the dissolution is preferably carried out under stirring. The stirring speed is not particularly limited, and the first metal salt can be completely dissolved.
In the invention, the temperature of the coordination reaction is preferably 140-200 ℃, more preferably 180 ℃; the time is preferably 4 to 12 hours, more preferably 8 hours.
After the coordination reaction, the precursor is preferably obtained by carrying out solid-liquid separation on the obtained feed liquid. In the present invention, the solid-liquid separation is preferably performed by centrifugation. The conditions for the centrifugation are not particularly limited, and centrifugation conditions well known to those skilled in the art may be employed.
In the present invention, the solid product after the solid-liquid separation is preferably washed and dried sequentially. In the present invention, the washing is preferably water washing; the drying mode is preferably vacuum drying; the drying temperature is preferably 60-80 ℃, and the drying time is preferably 8-10 h.
After the precursor is obtained, the precursor is dispersed in a second metal salt aqueous solution, and hydrolysis reaction is carried out, so that the multi-element metal hydroxide nano-sheet is obtained. In the present invention, the second metal salt in the second metal salt aqueous solution is preferably one or more of nitrate, chloride and acetate of a transition metal or a rare earth metal, more preferably acetate of a transition metal or acetate of a rare earth metal. In the present invention, the cation of the second metal salt in the second metal salt aqueous solution is different from the cation of the first metal salt. In the present invention, the transition metal in the second metal salt preferably includes one or more of nickel, cobalt, manganese, zinc, vanadium, molybdenum and copper, more preferably zinc. In the present invention, the rare earth metal preferably includes lanthanum and/or cerium. In a specific embodiment of the present invention, the second metal salt is preferably Zn (CH 3COO)2·2H2 O or Ce (NO 3)3·6H2 O).
In the invention, the solid-to-liquid ratio of the precursor and the second metal salt aqueous solution is preferably 1:0.5-1:10 mg/mL, more preferably 1:0.6mg/mL. In the present invention, the concentration of the second metal salt in the second metal salt aqueous solution is preferably 0.083 to 4.0mg/mL, more preferably 0.5 to 1.43mg/mL.
The precursor is dispersed in a second aqueous metal salt solution. In the present invention, the dispersing means is preferably ultrasonic dispersing; the dispersing time is preferably 8-10 min. The conditions of the ultrasonic dispersion are not particularly limited, and the second metal salt can be completely dispersed.
In the invention, the temperature of the hydrolysis reaction is preferably 90-180 ℃, more preferably 140-160 ℃; the time is preferably 2 to 10 hours, more preferably 4 to 5 hours. In the present invention, the coordination reaction and the hydrolysis reaction are preferably carried out independently in a stainless steel hot pot. In the present invention, the second metal salt undergoes a hydrolysis reaction (relatively weak) of the metal salt on the one hand, forming a hydroxide of the corresponding metal and releasing H +; on the other hand, the released H + etches the precursor generated by the coordination reaction to induce the original coordination bond to break, and also releases the corresponding metal ions to participate in the hydrolysis reaction, thereby forming the multi-element metal hydroxide nano-sheet.
After the hydrolysis reaction, the invention preferably carries out solid-liquid separation on the obtained feed liquid to obtain the multi-element metal hydroxide nano-sheet. In the present invention, the solid-liquid separation is preferably identical to the solid-liquid separation described above, and will not be described in detail herein. After the solid-liquid separation, the solid product after the solid-liquid separation is preferably washed and dried in sequence, and the washing and drying are preferably consistent with the washing and drying, and are not described in detail herein.
The invention also provides the multi-element metal hydroxide nano-sheet prepared by the preparation method.
In the present invention, the thickness of the multi-metal hydroxide nanosheets is preferably 2 to 10nm, more preferably 3.6 to 4.8nm, and even more preferably 4.4nm.
The invention also provides application of the multi-element metal hydroxide nano sheet in a super capacitor or a zinc ion battery.
For further explanation of the present invention, the multi-element metal hydroxide nanoplatelets provided in the present invention are described in detail below with reference to the accompanying drawings and examples, which should not be construed as limiting the scope of the present invention.
Example 1
Adding 87.3mg of Ni (NO 3)2·6H2 O and 43.4mg of Co (NO 3)2·6H2 O) into 70mL of isopropanol/glycerol mixed solvent (the volume ratio of isopropanol to glycerol is 8:1), stirring for 10min at room temperature to obtain pink transparent solution, transferring the pink transparent solution into a stainless steel hot pot, placing the stainless steel hot pot into a 180 ℃ heating box for coordination reaction for 8h at 180 ℃, taking out the stainless steel hot pot and cooling to room temperature after the reaction is finished, centrifuging the coordination reaction product, washing the centrifuged solid product with deionized water, and vacuum drying for 10h at 80 ℃ to obtain a bimetallic ion precursor;
15mg of Zn (CH 3COO)2·2H2 O is dissolved in 30mL of deionized water to obtain Zn 2+ ion aqueous solution, 30mg of the bimetallic ion precursor is placed in Zn 2+ ion aqueous solution to be dispersed for 8min in an ultrasonic way, the obtained dispersion is transferred into a stainless steel water heating kettle and is placed in a high-temperature reaction box, the reaction temperature is set to 160 ℃, the hydrolysis reaction is carried out for 5h under the condition of 160 ℃, after the reaction is finished, the stainless steel water heating kettle is taken out and cooled to room temperature, the hydrolysis reaction product is centrifuged, the centrifuged solid product is washed by deionized water, and the three-element metal ion hydroxide nano-sheet with the thickness of 3.6nm is obtained by vacuum drying at 80 ℃ for 10h, and is recorded as NiCoZn-OH nano-sheet.
Example 2
Adding 87.3mg of Ni (NO 3)2·6H2O、58.2mg Co(NO3)2·6H2 O and 25.1mg of Mn (NO 3)2·4H2 O) into 85mL of isopropanol/glycerol mixed solvent (the volume ratio of isopropanol to glycerol is 9:1), stirring for 10min at 26 ℃ to obtain pink transparent solution, transferring the pink transparent solution into a stainless steel hot pot, placing the stainless steel hot pot into a 180 ℃ heating box for coordination reaction for 8h at 180 ℃, taking out the stainless steel hot pot and cooling to room temperature after the reaction is finished, centrifuging the coordination reaction product, washing the centrifuged solid product with deionized water, and vacuum drying for 10h at 80 ℃ to obtain a ternary metal ion precursor;
30mg of Zn (CH 3COO)2·2H2 O is dissolved in 30mL of deionized water to obtain Zn 2+ ion aqueous solution, 50mg of ternary metal ion precursor is placed in Zn 2+ ion aqueous solution to be dispersed for 8min in an ultrasonic way, the obtained dispersion is transferred into a stainless steel water heating kettle and is placed in a high-temperature reaction box, the reaction temperature is set to be 140 ℃, hydrolysis reaction is carried out for 4h at the condition of 140 ℃, after the reaction is finished, the stainless steel water heating kettle is taken out and cooled to room temperature, the hydrolysis reaction product is centrifuged, the centrifuged solid product is washed by deionized water, and the obtained solid product is dried in vacuum for 10h at the condition of 80 ℃ to obtain the quaternary metal ion hydroxide nano-sheet with the thickness of 4.4nm, and the quaternary metal ion hydroxide nano-sheet is recorded as NiCoMnZn-OH nano-sheet.
Example 3
Adding 87.3mg of Ni (NO 3)2·6H2O、58.2mg Co(NO3)2·6H2 O and 25.1mg of Mn (NO 3)2·4H2 O) into 85mL of isopropanol/glycerol mixed solvent (the volume ratio of isopropanol to glycerol is 9:1), stirring for 10min at 26 ℃ to obtain pink transparent solution, transferring the pink transparent solution into a stainless steel hot pot, placing the stainless steel hot pot into a 180 ℃ heating box for coordination reaction for 8h at 180 ℃, taking out the stainless steel hot pot and cooling to room temperature after the reaction is finished, centrifuging the coordination reaction product, washing the centrifuged solid product with deionized water, and vacuum drying for 10h at 80 ℃ to obtain a ternary metal ion precursor;
43mg of Ce (NO 3)3·6H2 O is dissolved in 60mL of deionized water to obtain Ce 3+ ion aqueous solution, 100mg of ternary metal ion precursor is placed in Ce 3+ ion aqueous solution to be dispersed for 10min in an ultrasonic way, the obtained dispersion is transferred into a stainless steel water heating kettle and placed in a high-temperature reaction box, the reaction temperature is set to be 140 ℃, hydrolysis reaction is carried out for 4h at 140 ℃, after the reaction is finished, the stainless steel water heating kettle is taken out and cooled to room temperature, the hydrolysis reaction product is centrifuged, the centrifuged solid product is washed by deionized water, and the obtained solid product is dried in vacuum for 10h at 80 ℃ to obtain the quaternary metal ion hydroxide nano-sheet with the thickness of 4.8nm, which is recorded as NiCoMnCe-OH nano-sheet.
Test case
Scanning Electron Microscope (SEM), atomic Force Microscope (AFM) and X-ray diffraction (XRD) characterization tests were performed on NiCoMnZn-OH nanoplatelets prepared in example 2, and the results are shown below.
FIG. 1 is an SEM photograph of NiCoMnZn-OH nano-sheets prepared in example 2. As can be seen from the results in FIG. 1, the NiCoMnZn-OH nano-sheets prepared in the invention have typical nano-sheet morphology, and the NiCoMnZn-OH nano-sheets have obvious "wrinkles", which further indicates that the NiCoMnZn-OH nano-sheets prepared in the invention have the characteristic of smaller thickness.
FIG. 2 is an AFM photograph of NiCoMnZn-OH nanoplatelets prepared in example 2. As can be seen from the results in FIG. 2, niCoMnZn-OH nanoplatelets prepared in accordance with the present invention exhibit a typical lamellar structure.
FIG. 3 is an XRD spectrum of NiCoMnZn-OH nanoplatelets prepared in example 2. As can be seen from the results in FIG. 2, diffraction peaks occurring at 9.5 °, 33.7℃and 59.8℃belong to characteristic peaks of hydroxides, demonstrating that NiCoMnZn-OH nanoplatelets were successfully prepared in accordance with the present invention.
Application example
Placing the multi-element metal hydroxide nano-sheets prepared in the examples 1-3, acetylene black and polyvinylidene fluoride in an agate mortar according to a mass ratio of 7:2:1, dropwise adding 0.3mL of N-methyl pyrrolidone, fully grinding to obtain a pasty electrode coating material, uniformly coating the pasty electrode coating material on the surface of clean foam nickel, wherein the coating area is 1X 1cm 2, then vacuum drying for 24 hours at 80 ℃, flattening the coated foam nickel by adopting a pressure of 5MPa to obtain a working electrode, weighing the mass of the foam nickel before and after coating, and calculating the corresponding active material loading amount to be about 2-3 mg;
A three-electrode system was constructed with the working electrode, hg/HgO and platinum sheet prepared as described above, and a 3M KOH solution was used as the electrolyte to test the electrochemical properties of the multi-element metal hydroxide nanoplatelets, with the results shown below.
FIG. 4 is a CV test result of the NiCoZn-OH nano sheet prepared in example 1, and as can be seen from FIG. 4, a distinct oxidation-reduction peak exists in the charge-discharge process, and the typical Faraday electrochemical behavior and the characteristics of a "battery type" electrode material are shown; however, in the process of increasing the scanning rate from 2mV s -1 to 30mV s -1, the redox peak offset of the CV curve is obviously larger, and the polarization is more serious, which indicates that the rate capability of the electrode material is lower;
FIG. 5 shows the GCD test results of NiCoZn-OH nanoplatelets prepared in example 1. As can be seen from FIG. 5, the specific capacities at different current densities are 613 C g-1（1 A g-1）、594 C g-1（2 A g-1）、581.1 C g-1（3 A g-1）、561 C g-1（5 A g-1）、542.5 C g-1（7 A g-1）、522 C g-1（10 A g-1） and 450.1. 450.1C g -1（20 A g-1, respectively, and the corresponding capacity retention rate is 73.4% when the current density is increased from 1A g -1 to 20A g -1.
FIG. 6 is a Cyclic Voltammogram (CV) test result of NiCoMnZn-OH nanoplatelets prepared in example 2, and as can be seen from the result of FIG. 6, there is a distinct redox peak during charge and discharge, and typical Faraday electrochemical behavior and characteristics of "battery type" electrode materials are exhibited; meanwhile, the shape of the CV curve is almost unchanged in the process of increasing the scanning rate from 2mV s -1 to 30mV s -1, which further shows that the electrode material prepared by adopting the NiCoMnZn-OH nano sheet has higher rate capability.
Fig. 7 is a constant current charge-discharge (GCD) test result of NiCoMnZn-OH nanoplatelets prepared in example 2, and as can be seen from the result of fig. 7, the specific capacities at different current densities are 721 C g-1（1 A g-1）、704 C g-1（2 A g-1）、687.9 C g-1（3 A g-1）、678.5 C g-1（5 A g-1）、659.9 C g-1（7 A g-1）、629.2 C g-1（10 A g-1） and 587.6, C g -1（20 A g-1, respectively, and when the current density is increased from 1A g -1 to 20A g -1, the corresponding specific capacity retention rate is 81.5%, further confirming that the electrode material prepared by using NiCoMnZn-OH nanoplatelets has higher rate capability.
FIG. 8 is a CV test result of NiCoMnCe-OH nano-sheets prepared in example 3. As can be seen from FIG. 8, obvious redox peaks exist in the charge and discharge processes, and typical Faraday electrochemical behavior and characteristics of a battery type electrode material are shown; however, in the process of increasing the scanning rate from 2mV s -1 to 30mV s -1, the CV curve keeps a good shape and the redox peak offset is smaller, which indicates that the electrode material has higher rate capability;
Fig. 9 shows the GCD test results of NiCoMnCe-OH nanoplatelets prepared in example 3, and as can be seen from fig. 9, the specific capacities at different current densities are 665 C g-1（1 A g-1）、652.6 C g-1（2 A g-1）、642.3 C g-1（3 A g-1）、627.5 C g-1（5 A g-1）、617.4 C g-1（7 A g-1）、607 C g-1（10 A g-1） and 583 and C g -1（20 A g-1, respectively, and the corresponding capacity retention rate is 87.6% when the current density is increased from 1A g -1 to 20A g -1, which also shows that the prepared NiCoMnCe-OH electrode material has higher rate capability.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (10)
1. The preparation method of the multi-element metal hydroxide nano-sheet is characterized by comprising the following steps:
dissolving first metal salt in a polyol organic solvent to carry out coordination reaction to obtain a precursor;
dispersing the precursor in a second metal salt aqueous solution, and performing hydrolysis reaction to obtain the multi-element metal hydroxide nano-sheet;
the cations of the second metal salt in the second metal salt aqueous solution are different from the cations of the first metal salt;
The polyol organic solvent comprises an organic solvent and a polyol ligand; the volume ratio of the organic solvent to the polyol ligand is 10:1-5:1.
2. The method of claim 1, wherein the first metal salt is one or more of a nitrate, chloride and acetate of a transition metal; the transition metal includes one or more of nickel, cobalt, manganese, zinc, vanadium, molybdenum, and copper.
3. The method of claim 1, wherein the organic solvent comprises one or more of methanol, ethanol, isopropanol, N-dimethylformamide, acetone, and N-methylpyrrolidone; the polyol ligand is polyol with functionality more than or equal to 3.
4. The method according to any one of claims 1 to 3, wherein the ratio of the first metal salt to the polyol organic solvent is 14.55 to 698.4mg:32 to 362ml.
5. The method of claim 1, wherein the second metal salt in the aqueous solution of the second metal salt is one or more of nitrate, chloride and acetate of a transition metal or rare earth metal; the transition metal comprises one or more of nickel, cobalt, manganese, zinc, vanadium, molybdenum and copper; the rare earth metal comprises lanthanum and/or cerium.
6. The method of claim 1 or 5, wherein the precursor and the second aqueous metal salt solution are used in a ratio of 1:0.5 to 1:10mg/mL; the concentration of the second metal salt in the second metal salt aqueous solution is 0.083-4.0 mg/mL.
7. The preparation method according to claim 1, wherein the temperature of the coordination reaction is 140-200 ℃ and the time is 4-12 h.
8. The preparation method according to claim 1, wherein the hydrolysis reaction is carried out at a temperature of 90-180 ℃ for 2-10 hours.
9. The multi-element metal hydroxide nanoplatelets prepared by the preparation method of any one of claims 1 to 8.
10. Use of the multi-element metal hydroxide nanoplatelets of claim 9 in supercapacitors or zinc ion batteries.
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