CN113562716A - Solvothermal preparation of Zn0.5Ti2（PO4）3Method for preparing/C nano-flake negative electrode material - Google Patents
Solvothermal preparation of Zn0.5Ti2（PO4）3Method for preparing/C nano-flake negative electrode material Download PDFInfo
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002060 nanoflake Substances 0.000 title description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000011701 zinc Substances 0.000 claims abstract description 34
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000008367 deionised water Substances 0.000 claims abstract description 29
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000725 suspension Substances 0.000 claims abstract description 16
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 11
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 11
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002135 nanosheet Substances 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 6
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229960002303 citric acid monohydrate Drugs 0.000 claims abstract description 5
- 239000012046 mixed solvent Substances 0.000 claims abstract description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 15
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 10
- 229930006000 Sucrose Natural products 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000005720 sucrose Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 241000764238 Isis Species 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 7
- 235000016127 added sugars Nutrition 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- -1 polytetrafluoroethylene Polymers 0.000 description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 239000013049 sediment Substances 0.000 description 10
- 229910052593 corundum Inorganic materials 0.000 description 7
- 239000010431 corundum Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000000137 annealing Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 229960004106 citric acid Drugs 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910001414 potassium ion Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a solvothermal preparation method of Zn0.5Ti2(PO4)3A method for preparing a negative electrode material of a nanometer chip flower. Acetone and absolute ethyl alcohol are taken as mixed solvent, tetrabutyl titanate is added firstly, and then deionized water, zinc acetate dihydrate, ammonium dihydrogen phosphate and cane are sequentially addedSugar and citric acid monohydrate are stirred to obtain white suspension, then hydrothermal reaction is carried out, precipitate obtained by centrifugation is dried to obtain precursor, and the precursor is calcined to obtain Zn0.5Ti2(PO4)3the/C nanometer chip negative electrode material. The preparation method has simple preparation process and convenient operation, and the obtained Zn0.5Ti2(PO4)3the/C has the specific morphology of nano-sheet flowers, is a novel and simple battery negative electrode material, has a large specific surface area, and has excellent electrochemical performance.
Description
Technical Field
The invention relates to a potassium ion negative electrode material, in particular to a method for preparing Zn by solvothermal method0.5Ti2(PO4)3A method for preparing a nano-flake negative electrode material.
Background
Under the current large background of the world energy crisis and the ecological environment crisis, scientists all over the world are actively exploring new energy sources to replace fossil energy sources which are about to be exhausted, and have achieved remarkable achievements in the aspects of water energy, wind energy, tidal energy, solar energy and the like and practical application. In the field of electrochemistry, the development of lithium ion batteries is recognized by academia due to the advantages of high working specific capacity, light weight, long cycle life and the like, and the lithium ion batteries are put into use in large quantities and become mainstream batteries in the market at present. However, the mass application of lithium ion batteries requires a large supply of lithium resources, which are small in the world, account for only about 0.0065% of the earth's shell content, and are not uniformly distributed in the world. Potassium ions, as lithium ions and elements of the same main group, have similar physicochemical properties, more importantly, the reserves of potassium resources are very rich, and more scientific researches have focused on potassium ion batteries.
The NASICON (NATRIUM SUPER Ionic CONUCTOR) material has the advantages of environmental friendliness, stable structure, good cycle performance and the like, and is widely considered to be one of materials suitable for preparing battery electrodes. The titanium-based material is a common cathode material due to the characteristics of low charge-discharge platform, safety, no toxicity and the like. However, the application of the NASICON material is limited by the low charge-discharge specific capacity of the NASICON material, and the finding of a novel titanium-based material or the doping, coating and other operations of the novel titanium-based material are effective methods for improving the specific capacity at present.
New solvent thermal method as common preparationThe method for preparing the material has the characteristics of simple method, high synthesis efficiency, high operability and the like, and is favored by many scientific researchers. The invention synthesizes carbon-coated flaky Zn by relying on the basic principle of a solvothermal method0.5Ti2(PO4)3the/C shows excellent electrochemical performance and has important guiding significance for synthesizing novel titanium-based negative electrode materials.
Disclosure of Invention
The invention aims to provide a simple solvothermal preparation method of Zn aiming at the problems of poor electrochemical performance, complex synthesis method and the like of a titanium-based negative electrode material NASICON at the present stage0.5Ti2(PO4)3A method for preparing a negative electrode material of a nanometer chip flower.
The technical scheme of the invention is as follows:
solvothermal preparation of Zn0.5Ti2(PO4)3The method for preparing the/C nano-chip negative electrode material comprises the following steps:
(1) uniformly mixing acetone and absolute ethyl alcohol, obtaining a uniformly mixed solvent through magnetic stirring, dropwise adding n-butyl titanate under vigorous stirring, and sequentially adding deionized water, zinc acetate dihydrate, ammonium dihydrogen phosphate, sucrose and citric acid monohydrate after vigorous stirring;
(2) continuously carrying out magnetic stirring to obtain white turbid liquid;
(3) transferring the white suspension obtained in the step (2) into a high-pressure reaction kettle, reacting for 10-14 hours at 160-200 ℃, and naturally cooling to room temperature;
(4) removing supernatant from the reaction liquid obtained in the step (3), centrifuging the bottom precipitate by using deionized water and ethanol respectively, and drying to obtain offwhite Zn0.5Ti2(PO4)3a/C precursor powder;
(5) collecting Zn obtained in the step (4) by using a corundum ark0.5Ti2(PO4)3Putting the ark into a tube furnace after the/C precursor powder, and calcining under inert atmosphere (preferably pure argon atmosphere) to obtain Zn0.5Ti2(PO4)3C nanometer flowerAnd (3) a negative electrode material.
Further, in the step (1), the mass ratio of zinc acetate dihydrate, n-butyl titanate and ammonium dihydrogen phosphate is 0.9-1.1: 1.4-1.6: 3, and the mass ratio of deionized water, sucrose, citric acid monohydrate and n-butyl titanate is 13-16: 1.1-1.2: 1-1.1: 1.3 to 1.4 (more preferably 15: 1.1443: 1.0507: 1.35) of Zn0.5Ti2(PO4)3The mass ratio of carbon in the/C nanosheet flower-like material is 15-25%.
Further, in the step (1), the volume ratio of acetone to absolute ethyl alcohol to deionized water is 1: 0.9-1.2: 13-17; the volume ratio of n-butyl titanate to the mixed solvent is 1.1-1.5: 20 to 30.
Further, in the step (1), adding the n-butyl titanate for 20-40 minutes, and then adding the deionized water.
Further, in the step (2), the temperature of magnetic stirring is 50-70 ℃ and the time is 3 hours.
Further, in the step (4), the drying is vacuum drying, the drying temperature is 60-80 ℃, and the drying time is 4-6 hours.
Further, in the step (5), the calcination temperature is 600-.
It is worth mentioning that the inventors have surprisingly found during the course of experiments that, according to Zn, the method0.5Ti2(PO4)3Adding the materials according to the corresponding stoichiometric ratio (0.5:2:3) to obtain Zn0.5Ti2(PO4)3And the Zn feeding needs to be increased and the Ti feeding needs to be reduced at the same time, namely, the Zn feeding and the Ti feeding meet the requirement of 0.9-1.1: 1.4-1.6: 3 (more preferably 1:1.5:3), so that the product with excellent performance can be obtained.
The invention has the following technical effects:
the preparation method has simple preparation process and convenient operation, and the obtained Zn0.5Ti2(PO4)3the/C has the specific morphology of nano-sheet flowers, is a novel and simple battery negative electrode material, has a large specific surface area, and has excellent electrochemical performance.
Drawings
FIG. 1 shows Zn prepared in example 6 of the present invention0.5Ti2(PO4)3Scanning electron microscope image of/C nanoplatelets.
FIG. 2 shows Zn prepared in example 6 of the present invention0.5Ti2(PO4)3And the/C nano-sheet flower is used as a negative electrode material, and the potassium sheet is used as a counter electrode, so that the button cell is assembled. Under the temperature of 20-25 ℃, the current density is 0.05A g within the voltage range of 0.01-3.0V-1、0.1A g-1、0.2A g-1、0.3A g-1、1.0A g-1And 0.05A g-1And a multiplying power performance graph and a coulombic efficiency graph for carrying out charge and discharge tests.
FIG. 3 shows Zn prepared in example 6 of the present invention0.5Ti2(PO4)3And the/C nano-sheet flower is used as a negative electrode material, and the potassium sheet is used as a counter electrode, so that the button cell is assembled. 1.0A g at 20-25 deg.C and 0.01-3.0V-1A cycle life chart and a coulombic efficiency chart of the charge and discharge test under the current density of (1).
Detailed Description
The present invention will be described in further detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
The test methods in the following examples are conventional methods unless otherwise specified.
Example 1
Dropwise adding 1.32ml of n-butyl titanate into the lining of a high-pressure reaction kettle filled with 5ml of acetone and 5ml of absolute ethyl alcohol under vigorous stirring at 15-25 ℃, and stirring for 30min to obtain a clear transparent solution; then adding 15ml of deionized water, 0.5488g of zinc acetate dihydrate, 0.8627g of ammonium dihydrogen phosphate, 1.1443g of sucrose and 1.0507g of citric acid in sequence, and stirring for 3 hours at 60 ℃ to obtain milky white suspension; transferring the obtained milky white suspension into a high-pressure reaction kettle with a polytetrafluoroethylene lining and a capacity of 80mL, carrying out hydrothermal reaction for 12 hours at 180 ℃, and naturally cooling to room temperature; taking out the polytetrafluoroethylene lining, pouring out supernatant liquid inside, washing bottom sediment into a centrifugal tube by deionized water, centrifuging for 10min at 10000rpm, centrifuging and washing for three times by deionized water and ethanol respectively at the same centrifugal speed and time, collecting sediment, and vacuum drying at 60 ℃ for 6 hours to obtain offwhite powder. Collecting off-white powder by using a corundum ark, placing the ark in a tube furnace, putting the ark in the tube furnace filled with Ar and H2 mixed gas for sintering and annealing, wherein the specific calcining process is to heat the ark to 650 ℃ from room temperature, preserving heat for 6 hours, and then cooling the ark to room temperature to obtain the off-white powder material.
Example 2
Dropwise adding 1.32ml of n-butyl titanate into a 50ml beaker filled with 10ml of acetone and 5ml of absolute ethyl alcohol under vigorous stirring at 15-25 ℃, and stirring for 30min to obtain a clear transparent solution; then adding 15ml of deionized water, 0.5488g of zinc acetate dihydrate, 0.8627g of ammonium dihydrogen phosphate, 1.1443g of sucrose and 1.0507g of citric acid in sequence, and stirring for 3 hours at 70 ℃ to obtain milky white suspension; transferring the obtained milky white suspension into a high-pressure reaction kettle with a polytetrafluoroethylene lining and a capacity of 80mL, carrying out hydrothermal reaction for 12 hours at 180 ℃, and naturally cooling to room temperature; taking out the polytetrafluoroethylene lining, pouring out supernatant liquid inside, washing bottom sediment into a centrifugal tube by deionized water, centrifuging for 10min at 10000rpm, centrifuging and washing for three times by deionized water and ethanol respectively at the same centrifugal speed and time, collecting sediment, and vacuum drying at 60 ℃ for 6 hours to obtain offwhite powder. Collecting off-white powder by using a corundum ark, placing the ark in a tube furnace, putting the ark in the tube furnace filled with Ar and H2 mixed gas for sintering and annealing, wherein the specific calcining process is to heat the ark to 650 ℃ from room temperature, preserving heat for 6 hours, and then cooling the ark to room temperature to obtain the off-white powder material.
Example 3
At 15-25 ℃, under vigorous stirring, 1.7016ml of n-butyl titanate is dripped into a 50ml beaker filled with 5ml of acetone and 5ml of absolute ethyl alcohol, and a clear transparent solution is obtained after stirring for 30 min; then adding 15ml of deionized water, 0.5488g of zinc acetate dihydrate, 0.8627g of ammonium dihydrogen phosphate, 1.1443g of sucrose and 1.0507g of citric acid in sequence, and stirring for 5 hours at 70 ℃ to obtain milky white suspension; the resulting milky white suspension was transferred to a container of 80mLCarrying out hydrothermal reaction for 12 hours at 180 ℃ in a high-pressure reaction kettle with a polytetrafluoroethylene lining, and naturally cooling to room temperature; taking out the polytetrafluoroethylene lining, pouring out supernatant liquid inside, washing bottom sediment into a centrifugal tube by deionized water, centrifuging for 8min at 10000rpm, centrifuging and washing for three times by deionized water centrifugation and ethanol centrifugation respectively at the same centrifugation speed and time, collecting sediment, and vacuum drying at 60 ℃ for 6 hours to obtain offwhite powder. Collecting off-white powder with corundum ark, placing the ark in a tube furnace, introducing Ar and H2And (3) sintering and annealing in a mixed gas tube furnace, wherein the specific calcining process is to heat the mixed gas tube furnace from room temperature to 650 ℃, keep the temperature for 6 hours, and then cool the mixed gas tube furnace to room temperature.
Example 4
Dropwise adding 1.32ml of n-butyl titanate into a 50ml beaker filled with 5ml of acetone and 5ml of absolute ethyl alcohol at 15-25 ℃ under vigorous stirring, and stirring for 30min to obtain a clear transparent solution; then adding 15ml of deionized water, 0.5488g of zinc acetate dihydrate, 0.8627g of ammonium dihydrogen phosphate and 1.1443g of sucrose in sequence, and stirring for 3 hours at 60 ℃ to obtain milky white suspension; transferring the obtained milky white suspension into a high-pressure reaction kettle with a polytetrafluoroethylene lining and a capacity of 80mL, carrying out hydrothermal reaction for 12 hours at 180 ℃, and naturally cooling to room temperature; taking out the polytetrafluoroethylene lining, pouring out supernatant liquid inside, washing bottom sediment into a centrifugal tube by deionized water, centrifuging for 8min at 10000rpm, centrifuging and washing for three times by deionized water centrifugation and ethanol centrifugation respectively at the same centrifugation speed and time, collecting sediment, and vacuum drying at 60 ℃ for 6 hours to obtain offwhite powder. Collecting off-white powder with corundum ark, placing the ark in a tube furnace, introducing Ar and H2And (3) sintering and annealing in a mixed gas tube furnace, wherein the specific calcining process is to heat the mixed gas tube furnace from room temperature to 650 ℃, keep the temperature for 6 hours, and then cool the mixed gas tube furnace to room temperature.
Example 5
Dropwise adding 1.32ml of n-butyl titanate into a 50ml beaker filled with 5ml of acetone and 5ml of absolute ethyl alcohol at 15-25 ℃ under vigorous stirring, and stirring for 60min to obtain a clear transparent solution; then adding deionized water in sequence15ml of water, 0.5488g of zinc acetate dihydrate, 0.8627g of ammonium dihydrogen phosphate, 1.1443g of sucrose and 1.0507g of citric acid, stirring the mixture at 60 ℃ for 3 hours, adding 2.68g of urea, and reacting the mixture for 1 hour to obtain milky white suspension; transferring the obtained milky white suspension into a high-pressure reaction kettle with a polytetrafluoroethylene lining and a capacity of 80mL, carrying out hydrothermal reaction for 12 hours at 180 ℃, and naturally cooling to room temperature; taking out the polytetrafluoroethylene lining, pouring out supernatant liquid inside, washing bottom sediment into a centrifugal tube by deionized water, centrifuging for 10min at 10000rpm, centrifuging and washing for three times by deionized water and ethanol respectively at the same centrifugal speed and time, collecting sediment, and vacuum drying at 60 ℃ for 6 hours to obtain offwhite powder. Collecting off-white powder with corundum ark, placing the ark in a tube furnace, introducing Ar and H2And (3) sintering and annealing in a mixed gas tube furnace, wherein the specific calcining process is to heat the mixed gas tube furnace from room temperature to 650 ℃, keep the temperature for 6 hours, and then cool the mixed gas tube furnace to room temperature.
Example 6
Dropwise adding 1.32ml of n-butyl titanate into a 50ml beaker filled with 5ml of acetone and 5ml of absolute ethyl alcohol at 15-25 ℃ under vigorous stirring, and stirring for 30min to obtain a clear transparent solution; then adding 15ml of deionized water, 0.5488g of zinc acetate dihydrate, 0.8627g of ammonium dihydrogen phosphate, 1.1443g of sucrose and 1.0507g of citric acid in sequence, and stirring for 3 hours at 60 ℃ to obtain milky white suspension; transferring the obtained milky white suspension into a high-pressure reaction kettle with a polytetrafluoroethylene lining and a capacity of 80mL, carrying out hydrothermal reaction for 12 hours at 180 ℃, and naturally cooling to room temperature; taking out the polytetrafluoroethylene lining, pouring out supernatant liquid inside, washing the bottom precipitate into a centrifugal tube by using deionized water, centrifuging for 10min at 1000rpm, centrifuging and washing the bottom precipitate for three times by using the deionized water and ethanol respectively at the same centrifugal speed and time, collecting the precipitate, and drying the precipitate for 6 hours in vacuum at 60 ℃ to obtain the offwhite powder. Collecting off-white powder with corundum ark, placing the ark in a tube furnace, introducing Ar and H2And (3) sintering and annealing in a mixed gas tube furnace, wherein the specific calcining process is to heat the mixed gas tube furnace from room temperature to 650 ℃, keep the temperature for 6 hours, and then cool the mixed gas tube furnace to room temperature.
The products obtained in the above examples were used for characterization, and the product obtained in example 6 was used as an example (substantially uniform characterization results were obtained for the products obtained in other examples), and the obtained characterization results are shown below.
As shown in FIG. 1, Zn was produced0.5Ti2(PO4)3The nanometer sheet is very uniform and is about 150-250 nm, so that the potassium ions can be embedded/separated more favorably, and the electrochemical performance is good.
As shown in FIG. 2, Zn prepared by the present invention0.5Ti2(PO4)3And the/C nanosheet flower material is used as a negative electrode material, and the potassium sheet is used as a counter electrode, so that the button cell is assembled. Under the temperature of 20-25 ℃, the voltage range of 0.01-3.0V and different current density of 0.05Ag-1、0.1Ag-1、0.2Ag-1、0.3Ag-1、0.5Ag-1、1.0Ag-1And 0.05Ag-1The rate performance graph of the charge and discharge test was obtained. At 0.05A g-1The specific discharge capacity after 5 cycles of circulation is 252mAh g under the current density of-1When the current density increased to 0.1A g-1、0.2A g-1、0.4A g-1、0.8A g-1、1.0A g-1、2.0A g-1、3.0A g-1、5.0Ag-1When the discharge capacity is higher than the predetermined value, the discharge specific capacities are 228, 183, 165, 149 and 129 respectively, and the current density returns to 0.05Ag after the large-current charge and discharge-1Still have 219mAh g respectively-1Specific discharge capacity of (A) indicates Zn0.5Ti2(PO4)3the/C nanosheet flower material has good rate capability.
As shown in FIG. 3, Zn prepared by the present invention0.5Ti2(PO4)3And the/C nanosheet flower material is used as a negative electrode material, and the potassium sheet is used as a counter electrode, so that the button cell is assembled. 1.0Ag at 20-25 deg.C and 0.01-3.0V-1The first discharge specific capacity is 392mAh g-1The charging specific capacity is 128mAh g-1(ii) a The specific discharge capacity after 100 times of circulation is 131mAh g-1The charging specific capacity is 130mAh g-1(ii) a The specific discharge capacity after 200 times of circulation is 120mAh g-1The charging specific capacity is 119mAh g-1; the specific discharge capacity after 300 times of circulation is 131mAh g-1The charging specific capacity is 130mAh g-1(ii) a The specific discharge capacity after 300 times of circulation is 111mAh g-1The charging specific capacity is 110mAh g-1(ii) a The specific discharge capacity after 400 times of circulation is 105mAh g-1The charging specific capacity is 104mAh g-1(ii) a The specific discharge capacity after 500 times of circulation is 99mAh g-1And the charging specific capacity is 99mAh g-1. Indicates Zn0.5Ti2(PO4)3the/C nanosheet flower material has stable cycle performance.
Claims (7)
1. Solvothermal preparation of Zn0.5Ti2(PO4)3The method for preparing the/C nano-chip negative electrode material is characterized by comprising the following steps of:
(1) uniformly mixing acetone and absolute ethyl alcohol, dropwise adding tetrabutyl titanate under the stirring condition, sequentially adding deionized water, zinc acetate dihydrate, ammonium dihydrogen phosphate, sucrose and citric acid monohydrate after stirring, and continuously performing magnetic stirring to obtain a white suspension;
(2) transferring the white suspension obtained in the step (1) into a high-pressure reaction kettle, reacting at 160-200 ℃ for 10-14 hours, and naturally cooling to room temperature;
(3) removing supernatant from the reaction liquid obtained in the step (2), centrifuging the bottom precipitate by using deionized water and ethanol respectively, and drying to obtain offwhite Zn0.5Ti2(PO4)3a/C precursor powder;
(4) calcining the precursor powder obtained in the step (3) in an inert atmosphere to obtain Zn0.5Ti2(PO4)3the/C nanometer chip negative electrode material.
2. Solvothermal production of Zn according to claim 10.5Ti2(PO4)3The method for preparing the negative electrode material of the/C nanometer chip is characterized by comprising the following steps(1) In the method, the mass ratio of zinc acetate dihydrate, n-butyl titanate and ammonium dihydrogen phosphate is 0.9-1.1: 1.4-1.6: 3, and the mass ratio of deionized water, sucrose, citric acid monohydrate and n-butyl titanate is 13-16: 1.1-1.2: 1-1.1: 1.3 to 1.4, Zn obtained0.5Ti2(PO4)3The mass ratio of carbon in the/C nanosheet flower-like material is 15-25%.
3. Solvothermal production of Zn according to claim 10.5Ti2(PO4)3The method for preparing the/C nano chip negative electrode material is characterized in that in the step (1), the volume ratio of acetone to absolute ethyl alcohol to deionized water is 1: 0.9-1.2: 13-17; the volume ratio of n-butyl titanate to the mixed solvent is 1.1-1.5: 20 to 30.
4. Solvothermal production of Zn according to claim 10.5Ti2(PO4)3The method for preparing the/C nano-chip negative electrode material is characterized in that in the step (1), the n-butyl titanate is added for 20-40 minutes, and then the deionized water is added.
5. Solvothermal production of Zn according to claim 10.5Ti2(PO4)3The method for preparing the negative electrode material of the/C nanometer chip is characterized in that in the step (1), the temperature of magnetic stirring is 50-70 ℃ and the time is 2-4 hours.
6. Solvothermal production of Zn according to claim 10.5Ti2(PO4)3The method for preparing the/C nano chip negative electrode material is characterized in that in the step (3), the drying is vacuum drying, the drying temperature is 60-80 ℃, and the drying time is 4-6 hours.
7. Solvothermal production of Zn according to claim 10.5Ti2(PO4)3The method for preparing the/C nano-chip negative electrode material is characterized in that in the step (4), the calcining temperature is 600-650 ℃, the time is 3-6 h, and the heating rate isIs 3 to 5 ℃/min.
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