CN115241442A - Zirconium oxide coated potassium-doped lithium zinc titanate negative electrode material and preparation method thereof - Google Patents

Zirconium oxide coated potassium-doped lithium zinc titanate negative electrode material and preparation method thereof Download PDF

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CN115241442A
CN115241442A CN202211014952.XA CN202211014952A CN115241442A CN 115241442 A CN115241442 A CN 115241442A CN 202211014952 A CN202211014952 A CN 202211014952A CN 115241442 A CN115241442 A CN 115241442A
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mixed solution
negative electrode
electrode material
zirconium oxide
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曾宪光
龚靖
彭静
夏奎
黄开新
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Sichuan University of Science and Engineering
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Sichuan University of Science and Engineering
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a zirconium oxide coated potassium doped lithium zinc titanate negative electrode material and a preparation method thereof, wherein the chemical general formula of the zirconium oxide coated potassium doped lithium zinc titanate negative electrode material is as follows: li x K y ZnTi 3 O 8 @ZrO 2 Wherein x + y =2, y is more than 0 and less than 0.2, and the preparation method comprises the following steps: weighing anhydrous lithium acetate, dihydrate zinc acetate, nano titanium dioxide and potassium chloride according to a stoichiometric ratio, dissolving in anhydrous ethanol, and uniformly mixing to obtain a mixed solution A; heating and stirring the mixed solution A, and then drying and sintering to obtain Li x K y ZnTi 3 O 8 Powder; mixing Li x K y ZnTi 3 O 8 Dissolving the powder in deionized water, and uniformly mixing to obtain a mixed solution B; preparing zirconium acetate and citric acid into solutionDropwise adding the solution into the mixed solution B, and uniformly stirring to obtain a mixed solution C; putting the mixed solution C in a closed container to evaporate the solvent to obtain a white gelatinous substance, and then drying and sintering to obtain Li x K y ZnTi 3 O 8 @ZrO 2 . The cathode material obtained by the preparation method has good electronic conductivity and ionic conductivity and good electrochemical performance.

Description

Zirconium oxide coated potassium-doped lithium zinc titanate negative electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, and particularly relates to a zirconium oxide coated potassium doped lithium zinc titanate cathode material and a preparation method thereof.
Background
The lithium ion battery has the advantages of high specific energy, small volume, long cycle life, high working voltage and the like, and is widely applied. The cathode material as one of the important components of the lithium ion battery directly influences the electrochemical performance of the battery. Cubic lithium ion negative electrode material lithium zinc titanate Li 2 ZnTi 3 O 8 (LZTO) has the advantages of no toxicity, good safety, low cost, relatively high theoretical and low discharge voltage plateau (about 0.5V (vs. Li/Li) + ) Receive much attention. However, the LZTO has poor electron conductivity and thus has limited practical applications. Therefore, it is important to find a method for providing LZTO with good conductivity and ion conductivity.
At present, in order to overcome these defects, methods such as carbon coating, improvement of the manufacturing process, ion doping, and the like are generally used. The carbon material has the advantages of low price, high natural abundance, good conductivity, small dosage required by modification, stable physicochemical properties and the like, can obtain the high conductivity of the matrix material, and can reduce the side reaction between the electrode material and the electrolyte. Carbon coating is therefore considered to be a convenient modification to improve the conductivity of the electrode material. The structural nanocrystallization can increase the surface area of the material, which is beneficial to the sufficient penetration of the electrode material and the electrolyte. The ionic conductivity and the electronic conductivity of the LZTO can be improved by doping ions, and the electrochemical performance of the electrode material can be influenced by the doping position and the doping amount.
For example, in Li (Zeng X. G., et al Frontiers in Chemistry 2021, 8: 1-7) 2 ZnTi 3 O 8 Adding Cr (NO) 3 ) 3 By liquid phase method to realize Cr 3+ Doping of (3). The experimental result shows that the current density is 2 Ag −1 And 5A g −1 When Li is present 2 ZnTi 2.9 Cr 0.1 O 8 The specific discharge capacity of the anode is 156.7 mAh g -1 And 107.5 mAh g −1 . Furthermore, even at a current density of 1 ag −1 In the case of (1), after 200 cycles, the reversible specific capacity is still maintained at 162.2 mAh g −1 . It can be seen that Cr 3+ The doping of 2 ZnTi 2.9 Cr 0.1 O 8 Thereby improving its electrochemical performance.
There is also literature (Li Y., et al, ceramics International, 2021, 47 (13): 18732-18742) which prepares Li by a simple hydrothermal process 2 ZnTi 3 O 8 @α-Fe 2 O 3 A composite material. Li 2 ZnTi 3 O 8 /α-Fe 2 O 3 The composite material shows good compatibility with Li 2 ZnTi 3 O 8 Similar irregular spherical morphology and similar to original Li 2 ZnTi 3 O 8 Relatively small compared to the particle size. In all Li 2 ZnTi 3 O 8 /α-Fe 2 O 3 In the composite material, li 2 ZnTi 3 O 8 /α-Fe 2 O 3 The electrochemical performance of the composite (5 wt.%) is best. Li 2 ZnTi 3 O 8 /α-Fe 2 O 3 Composite (5 wt.%) at 1000 mA g −1 Has a reversible charge capacity of 184.8 mAh g when the cell is cycled 500 times at a current density of −1 And original Li 2 ZnTi 3 O 8 Providing only 110.7 mAh g -1 The reversible charging capacity of (2). Li 2 ZnTi 3 O 8 With alpha-Fe 2 O 3 Strong covalent bonds are formed between the two layers, which is favorable for reducing the interfacial energy and stabilizing the composite material. Due to special synergistic effects of multiphase interfaces, li 2 ZnTi 3 O 8 /α-Fe 2 O 3 The composite material not only has the advantages of a single component, but also exhibits novel and attractive properties, such as enhanced ionic conductivity, reduced interfacial charge transfer resistanceThe mobility of lithium ions is resisted and improved, and the rate capability and the reversible capacity are improved.
Although the electrochemical performance is improved by doping and cladding, the electrochemical performance of the prepared anode material is improved to a limited extent. Therefore, how to further improve the electrochemical performance of lithium zinc titanate is a technical problem that those skilled in the art expect to solve.
Disclosure of Invention
In view of the above-mentioned defects in the prior art, the present invention aims to provide a zirconium oxide coated potassium-doped lithium zinc titanate negative electrode material and a preparation method thereof, wherein the negative electrode material obtained by the preparation method has good electronic conductivity and ionic conductivity and good electrochemical performance.
The technical scheme of the invention is realized as follows:
a preparation method of a zirconium oxide coated potassium doped lithium zinc titanate negative electrode material is disclosed, wherein the chemical general formula of the zirconium oxide coated potassium doped lithium zinc titanate negative electrode material is as follows: li x K y ZnTi 3 O 8 @ZrO 2 Wherein x + y =2,0 < y < 0.2, and the preparation method comprises the following steps:
s1: weighing anhydrous lithium acetate, dihydrate zinc acetate, nano titanium dioxide and potassium chloride according to a stoichiometric ratio, dissolving in anhydrous ethanol, and uniformly mixing to obtain a mixed solution A for later use;
s2: heating and stirring the mixed solution A, and then drying and sintering to obtain Li x K y ZnTi 3 O 8 A powder;
s3: mixing Li x K y ZnTi 3 O 8 Dissolving the powder in deionized water, and uniformly mixing to obtain a mixed solution B for later use;
s4: preparing zirconium acetate and citric acid into a solution, and then dropwise adding the solution into the mixed solution B to be uniformly stirred to obtain a mixed solution C for later use;
s5: putting the mixed solution C in a closed container to evaporate the solvent to obtain a white gelatinous substance, and then drying and sintering to obtain the Li x K y ZnTi 3 O 8 @ZrO 2 。
Further, y =0.1.
Further, in the step S1, firstly, dissolving anhydrous lithium acetate, anhydrous zinc acetate and potassium chloride in anhydrous ethanol, carrying out ultrasonic treatment for 30-40 min, then adding nano titanium dioxide, and carrying out ultrasonic treatment for 30-40 min to obtain a mixed solution A.
Further, in step S2, the mixed solution A is heated and stirred at a temperature of 75 to 85 ℃, and a gel-like material is obtained after the solvent is volatilized.
Further, the gel-like material obtained in the step S2 is placed in an oven at 75-85 ℃ to be dried to obtain white powder, then the white powder is placed in a microwave sintering furnace, and sintering is carried out for 15-20 min at 700-750 ℃ in an argon atmosphere to obtain Li x K y ZnTi 3 O 8 And (3) powder.
Further, the mass ratio of zirconium acetate to citric acid was 1.
Further, in step S3, li x K y ZnTi 3 O 8 The mass volume ratio of the powder to the deionized water is 3 to 8 g:200 to 250 mL; in step S4, the mass of the zirconium acetate is Li x K y ZnTi 3 O 8 1 to 5% of the mass of the powder.
Further, in step S5, the mixed solution C is placed in a closed container and reacts for 2 to 3 hours at the temperature of 75 to 80 ℃ to obtain a white gel substance.
Further, in step S5, the white gel-like material is dried at 75 to 85 ℃ for 24 to 36 hours, then placed in a muffle furnace, and sintered at 400 to 450 ℃ for 5 to 6 hours, thereby obtaining Li x K y ZnTi 3 O 8 @ZrO 2 。
The invention also provides a zirconium oxide coated potassium doped lithium zinc titanate negative electrode material which is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention firstly adopts potassium chloride as a potassium source for doping and zirconium oxide coating modification on lithium zinc titanate, the radius of potassium ions is larger than that of lithium ions, and the addition of potassium ions can ensure that Li is added x K y ZnTi 3 O 8 The lattice constant of the powder increases, so that in Li x K y ZnTi 3 O 8 Defects are formed in the structure, and the formation of the defects is beneficial to improving the activity of the material and simultaneously widening the transmission channel of lithium ions. Then adopting zirconium acetate and citric acid solution in Li x K y ZnTi 3 O 8 The zirconia coating layer is prepared on the surface of the powder, the zirconia coating layer can effectively prevent the lithium zinc titanate from generating side reaction with electrolyte, and meanwhile, the zirconia can effectively control the size of the material and shorten the transmission distance of lithium ions, so that the electronic conductivity and the ionic conductivity of the material can be effectively improved, and the electrochemical performance of the lithium zinc titanate is further improved.
2. The invention adopts a microwave sintering method to prepare Li x K y ZnTi 3 O 8 Powder, which can be heated from both inside and outside directions, so that the Li is produced x K y ZnTi 3 O 8 The crystal grains of the powder are more uniform, thereby ensuring Li x K y ZnTi 3 O 8 @ZrO 2 While also contributing to a reduction in reaction time.
3. The invention selects zirconium acetate and citric acid as raw materials to prepare the zirconium oxide coating layer, the citric acid and the zirconium acetate are respectively dissolved in deionized water and then are mixed with Li x K y ZnTi 3 O 8 Mixing to ensure that zirconium acetate is uniformly coated on Li x K y ZnTi 3 O 8 The surface of the zirconium oxide is ensured to be formed in Li by the decomposition of the zirconium acetate x K y ZnTi 3 O 8 A uniform zirconia coating layer is formed on the surface.
Drawings
FIG. 1-Li prepared in example 2 1.9 K 0.1 ZnTi 3 O 8 @ZrO 2 XRD pattern of the material.
FIG. 2-Li prepared in example 2 1.9 K 0.1 ZnTi 3 O 8 @ZrO 2 HRTEM of material.
FIG. 3-Li 2 ZnTi 3 O 8 And example 2 preparationTo Li 1.9 K 0.1 ZnTi 3 O 8 And Li 1.9 K 0.1 ZnTi 3 O 8 @ZrO 2 Li prepared in example 4 1.85 K 0.15 ZnTi 3 O 8 And Li prepared in example 6 2 ZnTi 3 O 8 @ZrO 2 Cycling performance plot at 200mA/g current density.
FIG. 4-Li 2 ZnTi 3 O 8 And Li prepared in example 2 1.9 K 0.1 ZnTi 3 O 8 And Li 1.9 K 0.1 ZnTi 3 O 8 @ZrO 2 Li prepared in example 4 1.85 K 0.15 ZnTi 3 O 8 And Li prepared in example 6 2 ZnTi 3 O 8 @ZrO 2 The rate performance graph of (1).
FIG. 5-Li 2 ZnTi 3 O 8 And Li prepared in example 2 1.9 K 0.1 ZnTi 3 O 8 And Li 1.9 K 0.1 ZnTi 3 O 8 @ZrO 2 Li prepared in example 4 1.85 K 0.15 ZnTi 3 O 8 And Li prepared in example 6 2 ZnTi 3 O 8 @ZrO 2 Impedance graph of (a).
FIG. 6-Li 2 ZnTi 3 O 8 And Li prepared in example 2 1.9 K 0.1 ZnTi 3 O 8 And Li 1.9 K 0.1 ZnTi 3 O 8 @ZrO 2 Cyclic voltammogram of (a).
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Example 1
S1: 2.5076 g of anhydrous lithium acetate, 4.3900 g of zinc acetate dihydrate and 0.1491 g of potassium chloride are weighed and dissolved in 250ml of anhydrous ethanol, ultrasonic treatment is carried out for 30 min, then 4.7922 g of nano titanium dioxide is weighed and added into the solution, and ultrasonic treatment is carried out for 30 min, thus obtaining a mixed solution A.
S2: heating and stirring the mixed solution A at 80 ℃ until the solvent is volatilized to obtain a gel substance, and then drying in an oven at 80 ℃ for 24 hours; sintering the mixture for 15 min at 750 ℃ in a microwave sintering furnace in argon atmosphere to obtain Li 1.9 K 0.1 ZnTi 3 O 8 Powder;
s3: 0.6 g of Li was weighed 1.9 K 0.1 ZnTi 3 O 8 Dissolving the powder in 250mL of deionized water, and uniformly mixing to obtain a mixed solution B;
s4: weighing 0.006 g of zirconium acetate and 0.00352 g of citric acid, dissolving the zirconium acetate in the citric acid to prepare a solution, then dropwise adding the solution into the mixed solution B, and uniformly stirring to obtain a mixed solution C;
s5: the mixed solution C is subjected to a closed reaction at 80 ℃ for 3 h, then the solvent is evaporated to dryness, and then the mixed solution C is dried at 80 ℃ for 24 h and sintered at 400 ℃ in a muffle furnace for 5 h to obtain Li 1.9 K 0.1 ZnTi 3 O 8 @ZrO 2 。
Example 2
This example is the same as example 1 except that zirconium acetate was 0.018 g.
Example 3
This example is the same as example 1 except that zirconium acetate was 0.030 g in this example.
Example 4
The difference between this example and example 2 is that anhydrous lithium acetate is 2.44163 g, zinc acetate dihydrate is 4.3900 g, potassium chloride is 0.22365 g, and nano-titanium dioxide is 4.7922 g.
Example 5
The difference between this example and example 2 is that anhydrous lithium acetate is 2.57361 g, zinc acetate dihydrate is 4.3900 g, potassium chloride is 0.07455 g, and nano titanium dioxide is 4.7922 g.
Example 6
This example is the same as example 2 except that in this example, anhydrous lithium acetate was 2.6396 g, zinc acetate dihydrate was 4.3900 g, and nano-titanium dioxide was 4.7922 g, and potassium doping was not performed.
1. Example 2 preparation of Li 1.9 K 0.1 ZnTi 3 O 8 @ZrO 2 The XRD patterns of (A) are shown in figure 1, and it can be known from figure 1 that the 2 theta angles of 14.9 degrees, 18.3 degrees, 23.7 degrees, 26.0 degrees, 30.2 degrees, 35.0 degrees, 43.3 degrees, 50.0 degrees, 53.7 degrees, 57.2 degrees and 69.2 degrees respectively correspond to Li 2 ZnTi 3 O 8 The (110), (111), (210), (211), (220), (310), (004), (421), (422), (115) and (404) crystal planes of (II), and Li 2 ZnTi 3 O 8 The standard cards (PDF # 44-1037) basically conform to 2 theta angles of (111), (002) and (102) crystal planes of zirconia at 28.3 DEG, 31.5 DEG, 33.9 DEG and 35.78 DEG, respectively, and monoclinic zirconia (m-ZrO) 2 ) Standard cards (PDF # 80-0966) were substantially identical, indicating that monoclinic zirconia was produced.
2. Example 2 preparation of Li 1.9 K 0.1 ZnTi 3 O 8 @ZrO 2 As shown in FIG. 2, li can be found 1.9 K 0.1 ZnTi 3 O 8 @ZrO 2 The lattice fringes of the material are obvious, which shows that the crystallinity of the material is better. Calculating the interplanar spacing of the selected region to obtain that the interplanar spacing of the coating layer is 0.25 nm, which corresponds to the (102) crystal plane of the monoclinic zirconia, and is consistent with the XRD result, which shows that Li 1.9 K 0.1 ZnTi 3 O 8 @ZrO 2 The preparation is successful.
3. Li was prepared by the preparation of example 2 2 ZnTi 3 O 8 ，Li 2 ZnTi 3 O 8 And Li prepared in example 2 1.9 K 0.1 ZnTi 3 O 8 And Li 1.9 K 0.1 ZnTi 3 O 8 @ZrO 2 Li prepared in example 4 1.85 K 0.15 ZnTi 3 O 8 Li prepared in example 6 2 ZnTi 3 O 8 @ZrO 2 The cycle performance plot, the rate performance plot, and the impedance plot at a current density of 200mA/g are shown in fig. 3, 4, and 5, respectively:
as can be seen from FIG. 3, at 200mA g -1 The cycle performance test was performed at the current density of (1). On the second cycle, li 1.9 K 0.1 ZnTi 3 O 8 @ZrO 2 Specific capacity of 338.1 mAh g -1 And the specific capacity is 361.5 mAh g after 100 times of circulation -1 . Comparison of Li without Potassium doping 2 ZnTi 3 O 8 @ZrO 2 The specific discharge capacity after 100 times of circulation is 240.4 mAh g -1 ；Li 1.85 K 0.15 ZnTi 3 O 8 The specific discharge capacity after 100 times of circulation is 268.33 mAh g -1 . From this viewpoint, li 1.9 K 0.1 ZnTi 3 O 8 @ZrO 2 The cycle performance of (2) is optimal.
As can be seen from FIG. 4, li 1.9 K 0.1 ZnTi 3 O 8 @ZrO 2 At 50 mA g -1 Specific capacity at the second cycle of the current density of 413.9 mAh g -1 At 50 mA g -1 、100 mA g -1 、200 mA g -1 、500 mA g -1 And 1000 mA g -1 The specific capacity after 10 cycles was 424.9 mAh g -1 、410.7 mAh g -1 、394.1 mAh g -1 、337.6 mAh g -1 And 270.6 mAh g -1 . Comparison of Li without Potassium doping 2 ZnTi 3 O 8 @ZrO 2 At 50 mA g -1 、100 mA g -1 、200 mA g -1 、500 mA g -1 And 1000 mA g -1 The specific capacity after 10 cycles of each cycle was 245.6 mAh g -1 、239.7 mAh g -1 、226.3 mAh g -1 、207.8 mAh g -1 And 189.4 mAh g -1 ；Li 1.85 K 0.15 ZnTi 3 O 8 At 50 mA g -1 、100 mA g -1 、200 mA g -1 、500 mA g -1 And 1000 mA g -1 The specific capacity after 10 cycles was 308.05 mAh g -1 、281.77 mAh g -1 、258.51 mAh g -1 、233.8 mAh g -1 And 207.27 mAh g -1 . Viewed from this point, li 1.9 K 0.1 ZnTi 3 O 8 @ZrO 2 The rate capability of (2) is optimal.
As can be seen from FIG. 5, for Li 1.9 K 0.1 ZnTi 3 O 8 @ZrO 2 Performing AC impedance test, fitting, and testingThe charge transfer resistance was 68.51 Ω, vs. Li in example 6 without potassium doping 2 ZnTi 3 O 8 @ZrO 2 Has a charge transfer resistance of 242.1 Ω, in contrast to example 4, in which the doping is carried out at different stoichiometry ratios 1.85 K 0.15 ZnTi 3 O 8 The charge transfer resistance of (2) is 460.5 omega, thus showing that the resistance can be effectively reduced and the conductivity can be enhanced after the zirconium oxide is coated and modified while the potassium is doped.
4. Li was prepared by the preparation of example 2 2 ZnTi 3 O 8 ，Li 2 ZnTi 3 O 8 And Li prepared in example 2 1.9 K 0.1 ZnTi 3 O 8 And Li 1.9 K 0.1 ZnTi 3 O 8 @ZrO 2 Between 0.05 and 3V at 0.1 mV s -1 The redox potential differences were 195 mV, 143 mV, 114 mV respectively for cyclic voltammetry tests, from which it can be seen that: li 1.9 K 0.1 ZnTi 3 O 8 @ZrO 2 The redox potential difference is minimal and the polarization is minimal.
Finally, it should be noted that the above-mentioned examples of the present invention are only examples for illustrating the present invention, and are not intended to limit the embodiments of the present invention. Variations and modifications in other variations will occur to those skilled in the art upon reading the foregoing description. Not all embodiments are exhaustive. Obvious changes and modifications of the present invention are also within the scope of the present invention.

Claims (10)

1. The preparation method of the zirconium oxide coated potassium doped lithium zinc titanate negative electrode material is characterized in that the chemical general formula of the zirconium oxide coated potassium doped lithium zinc titanate negative electrode material is as follows: li x K y ZnTi 3 O 8 @ZrO 2 Wherein x + y =2,0 < y < 0.2, and the preparation method comprises the following steps:
s1: weighing anhydrous lithium acetate, dihydrate zinc acetate, nano titanium dioxide and potassium chloride according to a stoichiometric ratio, dissolving in anhydrous ethanol, and uniformly mixing to obtain a mixed solution A for later use;
s2: heating and stirring the mixed solution A, and then drying and sintering to obtain Li x K y ZnTi 3 O 8 Powder;
s3: mixing Li x K y ZnTi 3 O 8 Dissolving the powder in deionized water, and uniformly mixing to obtain a mixed solution B for later use;
s4: preparing zirconium acetate and citric acid into a solution, and then dropwise adding the solution into the mixed solution B to be uniformly stirred to obtain a mixed solution C for later use;
s5: putting the mixed solution C in a closed container to evaporate the solvent to obtain a white gelatinous substance, and then drying and sintering to obtain the Li x K y ZnTi 3 O 8 @ZrO 2 。
2. The preparation method of the zirconium oxide coated potassium doped lithium zinc titanate negative electrode material according to claim 1, wherein y =0.1.
3. The preparation method of the potassium-doped lithium zinc titanate negative electrode material coated with zirconium oxide according to claim 1, wherein in the step S1, anhydrous lithium acetate, zinc acetate dihydrate and potassium chloride are dissolved in anhydrous ethanol, and the solution is subjected to ultrasonic treatment for 30 to 40 min, then nanometer titanium dioxide is added, and the solution is subjected to ultrasonic treatment for 30 to 40 min, so that a mixed solution A is obtained.
4. The method for preparing the zirconium oxide coated potassium doped lithium zinc titanate negative electrode material as claimed in claim 1, wherein in step S2, the mixed solution A is heated and stirred at a temperature of 75-85 ℃, and a gel-like substance is obtained after the solvent is volatilized.
5. The preparation method of the zirconium oxide coated potassium doped lithium zinc titanate negative electrode material as claimed in claim 4, wherein the gel-like material obtained in the step S2 is dried in an oven at 75-85 ℃ to obtain white powder, and the white powder is placed in a microwave sintering furnace and subjected to argon sinteringSintering at 700 to 750 ℃ for 15 to 20 min in air atmosphere to obtain Li x K y ZnTi 3 O 8 And (3) powder.
6. The preparation method of the zirconium oxide coated potassium doped lithium zinc titanate negative electrode material according to claim 1, wherein the mass ratio of the zirconium acetate to the citric acid is 1.
7. The method for preparing the zirconium oxide coated potassium doped lithium zinc titanate negative electrode material according to claim 1, wherein in the step S3, li x K y ZnTi 3 O 8 The mass volume ratio of the powder to the deionized water is 3 to 8 g:200 to 250 mL; in step S4, the mass of zirconium acetate is Li x K y ZnTi 3 O 8 1 to 5% of the powder mass.
8. The preparation method of the zirconium oxide coated potassium doped lithium zinc titanate negative electrode material as claimed in claim 1, wherein in the step S5, the mixed solution C is placed in a closed container, and the reaction is carried out at 75 to 80 ℃ for 2 to 3 hours, so as to obtain a white gel-like substance.
9. The method for preparing the zirconium oxide coated potassium doped lithium zinc titanate negative electrode material as claimed in claim 1, wherein in step S5, the white gel-like material is dried at 75 to 85 ℃ for 24 to 36 hours, then placed in a muffle furnace, and sintered at 400 to 450 ℃ for 5 to 6 hours to obtain Li x K y ZnTi 3 O 8 @ZrO 2 。
10. A zirconium oxide coated potassium doped lithium zinc titanate negative electrode material, which is characterized by being prepared by the preparation method of any one of claims 1 to 9.
CN202211014952.XA 2022-08-23 2022-08-23 Zirconium oxide coated potassium-doped lithium zinc titanate negative electrode material and preparation method thereof Pending CN115241442A (en)

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