CN113277512A - Preparation of Ti with nano-scale ultrathin amorphous oxide layer by wet ball milling3C2Material, preparation method and application thereof - Google Patents
Preparation of Ti with nano-scale ultrathin amorphous oxide layer by wet ball milling3C2Material, preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 53
- 238000000498 ball milling Methods 0.000 claims abstract description 47
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 238000012986 modification Methods 0.000 claims abstract description 13
- 230000004048 modification Effects 0.000 claims abstract description 13
- 230000009471 action Effects 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims description 40
- 239000012046 mixed solvent Substances 0.000 claims description 19
- 239000003990 capacitor Substances 0.000 claims description 18
- 229910001415 sodium ion Inorganic materials 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 claims description 4
- 239000007784 solid electrolyte Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 7
- 238000000137 annealing Methods 0.000 abstract description 6
- 238000005245 sintering Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002194 amorphous carbon material Substances 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- -1 F127 Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical group [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/921—Titanium carbide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
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- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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Abstract
The invention discloses a method for preparing nano-scale superfine powder by wet ball millingThin amorphous oxide layer Ti3C2The material and the wet ball milling induce physical and chemical reactions by utilizing mechanical energy, and the materials are subjected to friction collision under the action of a certain medium, so that the tissue structure of the materials is changed to a certain extent. Compared with other preparation methods in the prior art, the method has the advantages of simple operation, simple process equipment and low production cost, and compared with the traditional method of introducing other material amorphous modification layers, such as wrapping amorphous carbon materials, obtaining the amorphous layer rich in defect active sites by sintering and annealing, the method not only avoids the inherent chemical energy barrier between the amorphous modification layer and the internal crystal lattice material, but also avoids the problem that the chemical stability in the circulation process is influenced by the collapse of the structure of the material after sintering and annealing.
Description
Technical Field
The invention relates to the technical field of synthesis of mixed sodium ion capacitor materials, in particular to a method for preparing Ti with a nanoscale ultrathin amorphous oxide layer by wet ball milling3C2A method for preparing the material.
Background
With the development of the electronic information era, people have urgent needs for searching sustainable energy, and the construction of clean and renewable energy storage devices becomes an urgent problem to be solved. Rechargeable batteries and capacitors are two complementary electrical energy storage devices that play a critical role in electric vehicle and electronic product development. Lithium ion batteries, the most mature rechargeable battery, have a strong competitive advantage in terms of energy density. However, lithium ion batteries have unsatisfactory power density and limited and uneven distribution of lithium resource reserves. An increasing number of researchers are turning to the development of other rechargeable batteries and capacitors. Capacitors have high power density, fast charge and discharge processes and long cycle life, but are limited by their lower energy density compared to rechargeable batteries. Hybrid ion capacitors have received much attention because they can combine the advantages of batteries and capacitors. Sodium-ion hybrid capacitors have a significant cost advantage over lithium-ion hybrid capacitors.
Sodium ion mixed electricityThe container mainly comprises a battery type positive electrode, a capacitance type negative electrode and a sodium salt electrolyte. Capacitive negative electrodes such as Nb2O5、TiO2、V2O5MXene has been widely researched, wherein MXene has high conductivity and large surface area, and has wide application prospect in pseudocapacitance electrodes. However, MXene stores sodium ions mainly in ion intercalation form, and is not satisfactory for ion adsorption type storage.
To address this issue, increasing MXene ionic sorption storage is the most effective strategy. We propose Ti with a nanoscale ultra-thin amorphous oxide layer3C2Method for preparing material, treated Ti3C2There is still a two-dimensional layered structure whose surface is coated with this nanoscale ultrathin oxide layer, which exists in an amorphous form. Therefore, the material structure increases the absorption and storage of sodium ions on the premise of not influencing the storage of ion embedding, accelerates the rapid charge transfer on the interface of an electrode and an electrolyte, is favorable for the diffusion of the sodium ions, and increases the pseudocapacitance of the capacitor.
Disclosure of Invention
The invention aims to prepare Ti with a nano-scale ultrathin amorphous oxide layer by wet ball milling3C2A method of preparing a material, which solves one or more of the above-mentioned problems of the prior art.
In order to solve the technical problem of the invention, the technical scheme is as follows: preparation of Ti with nano-scale ultrathin amorphous oxide layer by wet ball milling3C2Method for preparing material by controlling Ti3C2The amount of the titanium oxide is ball-milled with the mixed solvent for a period of time, and the oxide generated under the action of strong external force is tightly wrapped in a small layer of Ti3C2The crystal structure on the surface of the sheet is distorted to a certain degree, after ball milling for a period of time, deionized water or absolute ethyl alcohol is used for ultrasonic washing, and redundant solvents and oxides are washed away and dried; the Ti3C2The material is a few (1-3) Ti layers after stripping and etching3C2The quality of the grinding balls and the ball-milling materialThe weight ratio is 1-100:1, and the ball milling substance is Ti3C2A mixture with a mixed solvent, wherein the mixed solvent is a mixed solvent of a raw material solvent for synthesizing the oxide and a dispersing agent; mixing Ti3C2Slowly adding the stirred mixed solution; control of Ti3C2The mass ratio of the mixed solvent to the mixed solvent is 1: 1-100.
Preferably, the mixed solvent is ammonia water and Tetraethoxysilane (TEOS).
Preferably, the mixed solvent is Mn (CH)3COO)2·4H2O and deionized water.
Preferably, the dispersant is an inorganic dispersant or an organic dispersant.
Preferably, the oxide in the amorphous oxide layer is silicon dioxide, zinc oxide, aluminum oxide, manganese oxide, vanadium oxide.
Preferably, the ball milling speed is 100-.
Preferably, the stirring speed is 500-.
Preferably, the drying means can be room temperature air drying, 60-100 deg.C air blast oven drying for 12-24h, and freeze drying for 24-72 h.
In order to solve the technical problem of the invention, another technical scheme is provided as follows: the Ti with the nano-scale ultrathin amorphous oxide layer prepared by the method3C2A material.
In order to solve the technical problem of the invention, another technical scheme is provided as follows: the Ti with the nano-scale ultrathin amorphous oxide layer3C2The material application is that the nanometer ultra-thin amorphous oxide layer Ti is prepared by wet ball milling3C2The material can be used as a sodium ion capacitor, and the method can also be extended to be applied to electrode materials of other batteries or amorphous modification layers of solid electrolytes.
The invention provides a method for preparing Ti with a nano-scale ultrathin amorphous oxide layer by wet ball milling3C2Materials, including specific oxides and treatment methods corresponding thereto, by controlled ball milling of various solventsThe thickness, the lattice distortion degree and the like of the nanometer ultrathin amorphous oxide layer are regulated and controlled by proportion and concentration, ball milling time, a surfactant and the like.
Amorphous layer cathode materials with different thicknesses and degrees of lattice distortion are prepared by controlling the proportion and concentration of various solvents, ball milling time and surfactant. The thickness is regulated and controlled within a range from dozens of nanometers to several nanometers, the amorphous oxide layer refers to the typical crystal face spacing of the oxide, and the crystal lattice stripes are in disordered arrangement or even have no crystal lattice stripes.
By controlling Ti3C2The amount of the titanium oxide is ball-milled with various solvents for a period of time, and the oxide generated under the action of strong external force is tightly wrapped in a small layer of Ti3C2And (3) the crystal structure on the surface of the sheet is distorted to a certain degree, and after the surface of the sheet is ball-milled for a period of time, the surface of the sheet is ultrasonically washed by deionized water or absolute ethyl alcohol to wash away redundant solvents and oxides.
In the embodiment, Ti3C2Is etching Ti with HF3AlC2Washing and drying the Al layer by deionized water through dimethyl sulfoxide (DMSO) ultrasonic insertion to obtain few layers (1-3 layers) of Ti3C2。
In some embodiments, the synthesized oxide is one or more of silica, zinc oxide, alumina, manganese oxide, vanadium oxide, and the like.
In some embodiments, the dispersant is an inorganic dispersant, an organic dispersant, water. The inorganic dispersant is sodium pyrophosphate and sodium hexametaphosphate, and the organic dispersant is one or more of ethanol, polyacrylamide, F127, polyethylene glycol, etc.
In some embodiments, the ball milling conditions are that the ball milling speed is 100-: 1, the reaction time is 1-24 h.
In some embodiments, the stirring rate is 500-.
In some embodiments, Ti3C2The mass ratio of the solvent to the solvent is 1: 1-100.
In some embodiments, the drying means may be room temperature air drying, 60-100 deg.C forced air oven drying for 12-24h, and freeze drying for 24-72 h.
Preparation of Ti with nano-scale ultrathin amorphous oxide layer by wet ball milling3C2The material can be used in sodium ion capacitor, but not limited to sodium ion capacitor, the method can also be extended to be applied to electrode material of other batteries or amorphous modification layer of solid electrolyte.
The invention provides a method for preparing Ti with a nano-scale ultrathin amorphous oxide layer by wet ball milling3C2The material comprises specific oxide and a corresponding processing method, and the thickness, the lattice distortion degree and the like of the nanometer ultrathin amorphous oxide layer are regulated and controlled by controlling the proportion and the concentration of various ball milling solvents, the ball milling time, a surfactant and the like.
The nanometer level ultrathin amorphous oxide layer Ti with different thickness and lattice distortion degree is prepared by controlling the proportion and concentration of various solvents, ball milling time and surfactant3C2A material. The thickness is regulated and controlled within a range from dozens of nanometers to several nanometers, the amorphous oxide layer refers to the typical crystal face spacing of the oxide, and the crystal lattice stripes are in disordered arrangement or even have no crystal lattice stripes.
By controlling Ti3C2The amount of the titanium oxide is ball-milled with various solvents for a period of time, and the oxide generated under the action of strong external force is tightly wrapped in a small layer of Ti3C2And (3) the crystal structure on the surface of the sheet is distorted to a certain degree, and after the surface of the sheet is ball-milled for a period of time, the surface of the sheet is ultrasonically washed by deionized water or absolute ethyl alcohol to wash away redundant solvents and oxides.
The invention has the beneficial effects that:
1) the preparation method of the embodiment of the invention is that wet ball milling is carried out on Ti with a nano-scale ultrathin amorphous oxide layer3C2Compared with other preparation methods in the prior art, the method has the advantages of simple operation, simple process equipment and low production cost, and compared with the traditional method of introducing other material amorphous modification layers, such as amorphous layer rich in defect active sites obtained by wrapping amorphous carbon material, sintering and annealing, the method not only has the advantages of simple operation, simple process equipment and low production cost, but also has the advantages ofThe method avoids the inherent chemical energy barrier between the amorphous modification layer and the internal crystal lattice material and also avoids the problem that the chemical stability of the battery in the circulating process is influenced by the collapse of the structure of the material after sintering and annealing.
2) The invention prepares the Ti with the nano-scale ultrathin amorphous oxide layer by wet ball milling3C2The material can be used in sodium ion capacitor, but not limited to sodium ion capacitor, the method can also be extended to be applied to electrode material of other batteries or amorphous modification layer of solid electrolyte.
3) The invention prepares the Ti with the nano-scale ultrathin amorphous oxide layer by wet ball milling3C2Material, treated Ti3C2There is still a two-dimensional layered structure whose surface is coated with this nanoscale ultrathin oxide layer, which exists in an amorphous form. Therefore, the material structure increases the absorption and storage of sodium ions on the premise of not influencing the storage of ion embedding, accelerates the rapid charge transfer on the interface of an electrode and an electrolyte, is favorable for the diffusion of the sodium ions, and increases the pseudocapacitance of the capacitor.
4) By controlled ball milling of Ti3C2The proportion and concentration of the material and the raw material solvent for synthesizing the oxide, the ball milling time and the surfactant are used for preparing the nanometer ultrathin amorphous oxide layer Ti with different thicknesses and lattice distortion degrees3C2A material.
Drawings
FIG. 1 shows Ti as a raw material in example 1 of the present invention3C2SEM image of
FIG. 2 shows O-Ti obtained in example 1 of the present invention3C2SEM image of
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are only for illustrating the performance of the present invention more clearly and are not limited to the following examples.
Example 1:
preparation of Ti with nano-scale ultrathin amorphous oxide layer by wet ball milling3C2Preparation of the Material
Ti3C2The material is a few (1-3) Ti layers after stripping and etching3C2(gallop brocade science) 0.1g Ti3C2Dispersing in 2mL of absolute ethyl alcohol, performing ultrasonic treatment for half an hour, adding 0.25mL of ammonia water and 0.025mL of Tetraethoxysilane (TEOS) while stirring, uniformly mixing, performing ball milling at the stirring speed of 800rmp and the ball milling rotation speed of 800r/min for 12 hours, and mixing the grinding balls with the Ti3C2The mass ratio of the mixture to the mixed solvent is 100:1, repeatedly washing and centrifugally separating the grinding balls with 12 mm-diameter agate small balls for 3-5 times by using deionized water under the centrifugal condition of 8000rmp for 5min, and freeze-drying for 48h until the supernatant is neutral to obtain the final product with the nano-scale ultrathin amorphous oxide layer Ti3C2Material, noted as O-Ti3C2。
Assembling and testing the battery:
mixing O-Ti3C2The powder is uniformly mixed with conductive carbon black Super P and polyvinylidene fluoride PVDF according to the formula mass ratio of 8:1:1, and then the mixture is dripped into an N-methyl-2-pyrrolidone solvent. Fully stirring the mixture into slurry, and scraping the slurry on the carbon-coated aluminum foil by using a coating machine to obtain the pole piece. The coated pole piece was placed in an oven to dry overnight at 120 ℃. And then cutting the pole piece into a circular pole piece with the diameter of 11 mm. The glass fiber membrane is a diaphragm and contains 1.0M Na PF6The EMC solution as electrolyte is equipped into button cell in argon glove box, then activated and stood for 24h to test the performance of the cell on the cell test system.
FIG. 1 shows Ti as a raw material in example 1 of the present invention3C2SEM image of
FIG. 2 shows O-Ti obtained in example 1 of the present invention3C2SEM image of
O-Ti3C2Ultrathin amorphous oxide layer SiO with thickness of 5nm2As can be seen from XRD test, the XRD of the layer has a wide peak without crystal form, i.e. the transition amorphous modification layer O-Ti with specific thickness3C2The material exposes more ion channels, accelerating electrodes andthe rapid charge transfer on the electrolyte interface is beneficial to the diffusion of sodium ions, and the pseudocapacitance of the capacitor is increased on the premise of not influencing the intercalation of the sodium ions.
Example 2:
preparation of Ti with nano-scale ultrathin amorphous oxide layer by wet ball milling3C2Material
0.1g Ti3C20.034mg of Mn (CH) was added to 0.2mL of polyethylene glycol under stirring3COO)2·4H2O1.5 mL of deionized water, and carrying out ultrasonic treatment for 1h to obtain Ti3C2Modified by some Mn2+Further, 0.0145KMnO was added4Stirring and mixing uniformly, wherein the stirring speed is 800rmp, the ball milling rotating speed is 800r/min, the ball milling is carried out for 18 hours, and the grinding balls and the Ti are3C2The mass ratio of the mixture to the mixed solvent is 100:1, grinding balls are agate small balls with the diameter of 12mm, and the grinding balls and the Ti3C2Mass ratio of the mixture to the mixed solvent 150: 1, repeatedly washing and centrifugally separating the grinding balls with 12 mm-diameter agate small balls for 3-5 times by using deionized water under the centrifugal condition of 8000rmp for 5min, and freeze-drying for 48h until the supernatant is neutral to obtain the final product with the nano-scale ultrathin amorphous oxide layer Ti3C2Material, noted M-Ti3C2。
Assembling and testing the battery:
mixing M-Ti3C2The powder is uniformly mixed with conductive carbon black Super P and polyvinylidene fluoride PVDF according to the formula mass ratio of 8:1:1, and then the mixture is dripped into an N-methyl-2-pyrrolidone solvent. Fully stirring the mixture into slurry, and scraping the slurry on the carbon-coated aluminum foil by using a coating machine to obtain the pole piece. The coated pole piece was placed in an oven to dry overnight at 120 ℃. And then cutting the pole piece into a circular pole piece with the diameter of 11 mm. The glass fiber membrane is a diaphragm and contains 1.0M Na PF6The EMC solution as electrolyte is equipped into button cell in argon glove box, then activated and stood for 24h to test the performance of the cell on the cell test system.
M-Ti3C2MnO with thickness of 12nm and ultrathin amorphous oxide layer2The transition amorphous modification layer M-Ti with a specific thickness3C2The material exposes more ion channels, accelerates the rapid charge transfer on the interface of the electrode and the electrolyte, is beneficial to the diffusion of sodium ions, and increases the pseudo capacitance of the capacitor on the premise of not influencing the intercalation of the sodium ions.
The embodiment provided by the invention provides a method for preparing Ti with a nano-scale ultrathin amorphous oxide layer by wet ball milling3C2The wet ball milling utilizes mechanical energy to induce physical and chemical reactions, and generates friction collision under the action of a certain medium, so that the tissue structure of the material is changed to a certain extent. Compared with other preparation methods in the prior art, the method has the advantages of simple operation, simple process equipment and low production cost, and compared with the traditional method of introducing other material amorphous modification layers, such as wrapping amorphous carbon materials, obtaining the amorphous layer rich in defect active sites by sintering and annealing, the method not only avoids the inherent chemical energy barrier between the amorphous modification layer and the internal crystal lattice material, but also avoids the problem that the chemical stability in the battery circulation process is influenced by the collapse of the structure of the material after sintering and annealing.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these should also be construed as being within the scope of the present invention.
Claims (10)
1. Preparation of Ti with nanoscale ultrathin amorphous oxide layer by wet ball milling3C2The preparation method of the material is characterized by comprising the following steps: by controlling Ti3C2The amount of the titanium oxide is ball-milled with the mixed solvent for a period of time, and the oxide generated under the action of strong external force is tightly wrapped in a small layer of Ti3C2The crystal structure on the surface of the sheet is distorted to a certain degree, after ball milling for a period of time, deionized water or absolute ethyl alcohol is used for ultrasonic washing, and redundant solvents and oxides are washed away and dried; the Ti3C2The material is stripped and etchedA few (1 to 3) layers of Ti3C2The mass ratio of the grinding balls to the ball-milling material is 1-100:1, and the ball-milling material is Ti3C2A mixture with a mixed solvent, wherein the mixed solvent is a mixed solvent of a raw material solvent for synthesizing the oxide and a dispersing agent; mixing Ti3C2Slowly adding the stirred mixed solution; control of Ti3C2The mass ratio of the mixed solvent to the mixed solvent is 1: 1-100.
2. The preparation of Ti with nanoscale ultra-thin amorphous oxide layer by wet ball milling according to claim 13C2The preparation method of the material is characterized by comprising the following steps: the mixed solvent is ammonia water and Tetraethoxysilane (TEOS).
3. The preparation of Ti with nanoscale ultra-thin amorphous oxide layer by wet ball milling according to claim 13C2The preparation method of the material is characterized by comprising the following steps: the mixed solvent is Mn (CH)3COO)2·4H2O and deionized water.
4. The preparation of Ti with nanoscale ultra-thin amorphous oxide layer by wet ball milling according to claim 13C2The preparation method of the material is characterized by comprising the following steps: the dispersant is an inorganic dispersant or an organic dispersant.
5. The preparation of Ti with nanoscale ultra-thin amorphous oxide layer by wet ball milling according to claim 13C2The preparation method of the material is characterized by comprising the following steps: the oxide in the amorphous oxide layer is silicon dioxide, zinc oxide, aluminum oxide, manganese oxide and vanadium oxide.
6. The preparation of Ti with nanoscale ultra-thin amorphous oxide layer by wet ball milling according to claim 13C2The preparation method of the material is characterized by comprising the following steps: the ball milling speed is 100-1800r/min, and the ball milling reaction time is 1-24 h.
7. The preparation of Ti with nanoscale ultra-thin amorphous oxide layer by wet ball milling according to claim 13C2The preparation method of the material is characterized by comprising the following steps: the stirring speed is 500-1000r/min, and the reaction time is 1-24 h.
8. The preparation of Ti with nanoscale ultra-thin amorphous oxide layer by wet ball milling according to claim 13C2The preparation method of the material is characterized by comprising the following steps: the drying means can be room temperature air drying, 60-100 deg.C air blast oven drying for 12-24h, and freeze drying for 24-72 h.
9. Ti with nanoscale ultrathin amorphous oxide layer prepared by the method of any one of claims 1 to 83C2A material.
10. The Ti with nanoscale ultra-thin amorphous oxide layer of claim 93C2Material application, characterized in that: preparation of Ti with nano-scale ultrathin amorphous oxide layer by wet ball milling3C2The material can be used as a sodium ion capacitor, and the method can also be extended to be applied to electrode materials of other batteries or amorphous modification layers of solid electrolytes.
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