CN114388752A - Chain-like fiber structure lithium titanate compound and preparation method and application thereof - Google Patents

Chain-like fiber structure lithium titanate compound and preparation method and application thereof Download PDF

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CN114388752A
CN114388752A CN202111501179.5A CN202111501179A CN114388752A CN 114388752 A CN114388752 A CN 114388752A CN 202111501179 A CN202111501179 A CN 202111501179A CN 114388752 A CN114388752 A CN 114388752A
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lithium
source material
lithium titanate
titanium source
solution
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周若
刘洋
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Gree Altairnano New Energy Inc
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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
    • H01M4/48—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention relates to the technical field of lithium batteries, and discloses a chain-like fiber structure lithium titanate compound and a preparation method and application thereof. The composite comprises a lithium source material, a titanium source material and zinc acetate. According to the invention, a lithium source material, a titanium source material and zinc acetate are used as raw materials, a lithium titanate composite precursor is prepared by adopting a sol-gel process and an electrostatic spinning process, and then the lithium titanate composite with a chain-like fiber structure is obtained by high-temperature calcination. Through specific raw materials and processes, the prepared chain-like fiber structure lithium titanate composite has higher specific capacity, increases the specific surface area of the lithium titanate material, improves the rate capability, has more excellent performance compared with spinel lithium titanate and other similar materials, and can be widely applied to the preparation of lithium batteries.

Description

Chain-like fiber structure lithium titanate compound and preparation method and application thereof
Technical Field
The application relates to the technical field of lithium batteries, in particular to a chain-like fiber structure lithium titanate compound and a preparation method and application thereof.
Background
Along with the continuous progress of current social science and technology, the world demand for clean energy is continuously improved, and lithium ion batteries are more and more widely applied to various scenes of life due to the advantages of high energy density, no environmental pollution and the like. Graphite electrodes are generally used in traditional lithium ion batteries, but graphite electrodes have great potential safety hazards and cycle performance in the using process, and compared with spinel lithium titanate (Li)4Ti5O12) Many of these materials are availableThe charging and discharging platform has the advantages of high charging and discharging level platform position, good safety performance, no change of charging and discharging volume and the like. However, the theoretical capacity of lithium titanate is 175mAh/g, the theoretical capacity of graphite is 372mAh/g, the electronic conductivity of lithium titanate is low, and flatulence is easy to occur in the charging and discharging processes. In order to improve the defects, the surface of lithium titanate is generally coated with carbon, or lithium titanate is subjected to ion doping, or lithium titanate is subjected to shape modification.
Disclosure of Invention
In view of the above, the present invention aims to provide a lithium titanate composite with a chain-like fiber structure and a preparation method thereof, such that the composite has high capacity and excellent rate capability and cycle performance.
Another object of the present invention is to provide a lithium battery prepared based on the above composite and its use in the preparation of lithium batteries.
To solve the above technical problem/achieve the above object or at least partially solve the above technical problem/achieve the above object, the present invention provides a chain-like fiber structure lithium titanate composite including a lithium source material, a titanium source material, and zinc acetate.
Aiming at the problems of capacity and rate of the lithium titanate material, the lithium titanate composite precursor is prepared by taking a lithium source material, a titanium source material and zinc acetate as raw materials and combining a sol-gel method with electrostatic spinning, and then the lithium titanate composite precursor is calcined at high temperature to obtain the lithium titanate composite.
Preferably, the lithium source material, the titanium source material and the zinc acetate are in terms of molar ratios of Li, Ti and Zn, where Li: ti: zn+(0.8-0.85): 1:(0.01-0.05). In a specific embodiment of the present invention, the lithium source material, the titanium source material, and the zinc acetate are in terms of a molar ratio of Li, Ti, and Zn, where Li: ti: zn+＝0.82：1：0.01。
Preferably, the lithium source material is one or more of lithium acetate, lithium hydroxide and lithium carbonate; the titanium source material is one or more than two of tetrabutyl titanate, titanium tetrachloride and n-propyl titanate. In a specific embodiment of the present invention, the lithium source material is lithium acetate, and the titanium source material is tetrabutyl titanate.
Zn doped prepared by the invention+The lithium titanate composite material has the advantages that due to the fact that the temperature is too high during calcination, organic matters are decomposed too fast, the shape is a chain-shaped fiber structure, a large number of folds are formed on the surface of a fiber filament, the specific surface area of lithium titanate is increased, and the rate capability is improved. The discharge capacity of a button lithium ion battery prepared by the composite lithium titanate material under the multiplying power of 1C is 199mAh/g, the capacity is still 176mAh/g after 50 times of circulation, and the specific capacity of the lithium titanate material is greatly improved; and then, carrying out rate performance tests on the button battery with stable performance under the conditions of 0.5C, 1C, 2C and 3C, wherein the specific capacities are 182mAh/g, 160mAh/g, 142mAh/g and 134mAh/g in sequence, and the recovery test can keep about 95% of the specific capacity. The invention therefore proposes the use of said composite for the production of lithium batteries.
According to the application, the invention provides a lithium battery, which takes the composite as an electrode active material and can be used for preparing a positive electrode or a negative electrode and assembling the lithium battery.
In addition, the invention also provides a preparation method of the compound, which comprises the following steps:
step 1, preparing an electrostatic spinning solution containing a lithium source material, a titanium source material, zinc acetate, an organic solvent and a dispersing agent;
step 2, preparing a lithium titanate compound precursor by electrostatic spinning;
and 3, calcining the lithium titanate compound precursor at high temperature to obtain the compound.
Preferably, step 1 is:
dissolving a titanium source material in glacial acetic acid to prepare a titanium source solution; dissolving an organic solvent in a dispersing agent to obtain an organic solvent solution, pouring a titanium source solution into the organic solvent solution, stirring, adding a lithium source material and zinc acetate, and continuing stirring until a transparent sol-gel solution, namely the electrostatic spinning solution, is obtained. In a specific embodiment of the present invention, the organic solvent is polyvinylpyrrolidone, and the dispersant is ethanol and/or acetone.
Preferably, step 2 is to place the electrospinning solution in an injector of an electrospinning device, and perform electrospinning under the condition of a direct-current high-voltage electric field to prepare a white fibrous felt-like lithium titanate composite precursor.
Preferably, step 3, putting the lithium titanate composite precursor into a muffle furnace for high-temperature calcination to prepare a chain-like fiber structure lithium titanate composite; specifically, the high-temperature calcination is carried out for 1h-2h at 700-900 ℃.
According to the technical scheme, the lithium titanate composite with the chain-like fiber structure is prepared by taking a lithium source material, a titanium source material and zinc acetate as raw materials, adopting a sol-gel process and an electrostatic spinning process to prepare a lithium titanate composite precursor, and then calcining at high temperature. Through specific raw materials and processes, the prepared chain-like fiber structure lithium titanate composite has higher specific capacity, increases the specific surface area of the lithium titanate material, improves the rate capability, has more excellent performance compared with spinel lithium titanate and other similar materials, and can be widely applied to the preparation of lithium batteries.
Drawings
FIG. 1 is a graph showing the morphology of the particles of example 1;
FIG. 2 is a graph showing the cycle performance of example 1;
FIG. 3 is a graph showing rate capability of example 1;
FIG. 4 is a graph showing the cycle performance of comparative example 1;
FIG. 5 is a graph showing the rate performance of comparative example 1;
FIG. 6 is a particle morphology map of comparative example 2;
FIG. 7 is a graph showing the rate performance of comparative example 2;
fig. 8 is a graph showing the cycle performance of comparative example 2.
Detailed Description
The invention discloses a chain-like fiber structure lithium titanate compound, a preparation method and application thereof, and a person skilled in the art can appropriately improve process parameters by referring to the content. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the products, processes and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations and modifications, or appropriate alterations and combinations, of the products, processes and applications described herein may be made and used without departing from the spirit, scope and ambit of the invention. It should be apparent that the described embodiments are only some of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
It is noted that, in this document, relational terms such as "first" and "second", "step 1" and "step 2", and "(1)" and "(2)" are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The invention specifically provides a preparation method of a chain-shaped fiber structure lithium titanate compound and a compound prepared by the preparation method, and the method comprises the following steps:
1) mixing a lithium source material, a titanium source material and zinc acetate according to a certain proportion by using a sol-gel method to prepare a spinning solution;
dissolving a titanium compound in glacial acetic acid to prepare a titanium source solution; dissolving polyvinylpyrrolidone in a dispersing agent to obtain a polyvinylpyrrolidone solution, pouring a titanium source solution into the polyvinylpyrrolidone solution, stirring for a period of time, adding zinc acetate and a lithium source material, and continuing stirring until a transparent sol-gel solution is obtained, wherein the solution is an electrostatic spinning solution.
Wherein the molar ratio of the lithium source material to the titanium source material to the zinc acetate is Li: ti: zn molar ratio 0.82: 1: 0.01; the lithium source material is lithium acetate, lithium hydroxide, lithium carbonate and the like, and the titanium source material is tetrabutyl titanate, titanium tetrachloride, n-propyl titanate and the like; the dispersant is ethanol, acetone, etc.
2) Spinning the spinning solution in a direct-current high-voltage electric field to prepare a lithium titanate composite precursor;
and (3) placing the spinning solution in an injector of an electrostatic spinning device, and carrying out electrostatic spinning under the condition of a direct-current high-voltage electric field to prepare a white fibrous felt-like lithium titanate composite precursor.
3) And putting the lithium titanate compound precursor into a muffle furnace for heat treatment to obtain the lithium titanate compound.
Putting the lithium titanate composite precursor into a muffle furnace, and calcining for 1-2 h at 700-900 ℃ to prepare the chain-like fiber structure lithium titanate composite.
According to the invention, the comparison of the control compound without adding zinc acetate and replacing zinc acetate with zinc nitrate is carried out in the specific implementation mode, and the result shows that the zinc nitrate group compound can not form a chain-shaped fiber structure, and the cycle performance and the rate performance are poor; and the specific capacity of the lithium titanate without the lithium titanate is poor.
In each group comparison experiment provided by the invention, unless particularly stated, other experiment conditions, materials and the like are consistent except for the differences indicated by each group so as to have comparability.
The invention further provides a chain-like fiber structure lithium titanate composite, a preparation method and an application thereof.
Example 1: preparing the chain-like fiber structure lithium titanate compound
According to mol ratio of Li: ti: zn+0.82: 1: weighing lithium acetate and titanium in a proportion of 0.01Tetrabutyl titanate and zinc acetate, 0.01mol of tetrabutyl titanate is dissolved in 1ml of glacial acetic acid and stirred to prepare a titanium source solution; dissolving 10g of polyvinylpyrrolidone in 15ml of ethanol, stirring for 1h to obtain a polyvinylpyrrolidone solution, pouring the titanium source solution into the polyvinylpyrrolidone solution, stirring for a period of time, adding zinc acetate and lithium acetate, and continuing stirring until a transparent spinning solution is obtained. Placing the spinning solution in an injector of an electrostatic spinning device, and carrying out electrostatic spinning in a 28Kv direct-current high-voltage electric field to prepare the Zn-doped material+A lithium titanate precursor. Will be doped with Zn+Putting the lithium titanate precursor into a muffle furnace to calcine for 2 hours at the high temperature of 800 ℃ to prepare Zn-doped lithium titanate+The particle morphology of the lithium titanate composite is shown in figure 1, and due to the fact that the temperature is too high during calcination, the organic matter is decomposed too fast, the morphology is a chain-shaped fiber structure, the surface of a fiber filament is provided with a large number of folds, and the specific surface area of lithium titanate is increased. The invention is characterized in that Li: ti: zn+(0.8-0.85): 1, (0.01-0.05) the preparation is carried out for a plurality of times in different proportions, the particle morphology graph is similar to that of the particle morphology graph shown in figure 1 and is of a chain-shaped fiber structure, the surface of the fiber filament is provided with a large number of folds, and the specific surface area of lithium titanate is increased.
Example 2: lithium titanate prepared without adding zinc acetate and lithium titanate compound adopting zinc nitrate to replace zinc acetate
1. Comparative example
Comparative example 1 no zinc acetate was added based on example 1; comparative example 2 replacement of zinc acetate with zinc nitrate on the basis of example 1;
2. experimental methods
Comparative example 1
According to mol ratio of Li: ti ═ 0.82: 1, weighing lithium acetate and tetrabutyl titanate according to the proportion of 1, dissolving 0.01mol of tetrabutyl titanate in 1ml of glacial acetic acid, and stirring to prepare a titanium source solution; dissolving 10g of polyvinylpyrrolidone in 15ml of ethanol, stirring for 1h to obtain a polyvinylpyrrolidone solution, pouring the titanium source solution into the polyvinylpyrrolidone solution, stirring for a period of time, adding lithium acetate, and continuing stirring until a transparent spinning solution is obtained. And (3) placing the spinning solution in an injector of an electrostatic spinning device, and carrying out electrostatic spinning in a 28Kv direct-current high-voltage electric field to prepare a lithium titanate precursor.
Comparative example 2
According to mol ratio of Li: ti: zn+0.82: 1: weighing lithium acetate, tetrabutyl titanate and zinc nitrate according to the proportion of 0.01, dissolving 0.01mol of tetrabutyl titanate in 1ml of glacial acetic acid, and stirring to prepare a titanium source solution; dissolving 10g of polyvinylpyrrolidone in 15ml of ethanol, stirring for 1h to obtain a polyvinylpyrrolidone solution, pouring the titanium source solution into the polyvinylpyrrolidone solution, stirring for a period of time, adding zinc nitrate and lithium acetate, and continuing stirring until a transparent spinning solution is obtained. Placing the spinning solution in an injector of an electrostatic spinning device, and carrying out electrostatic spinning in a 28Kv direct-current high-voltage electric field to prepare the Zn-doped material+A lithium titanate precursor.
(3) Measurement results
The cycling performance and rate performance of the button cell prepared in example 1 are shown in fig. 2 and 3. The discharge capacity of the lithium ion battery prepared from the composite lithium titanate material under the multiplying power of 1C is 199mAh/g, the capacity is still 176mAh/g after circulation for 50 times, and the specific capacity of the lithium titanate material is greatly improved. And then, carrying out rate performance tests on the button battery with stable performance under the conditions of 0.5C, 1C, 2C and 3C, wherein the specific capacities are 182mAh/g, 160mAh/g, 142mAh/g and 134mAh/g in sequence, and the recovery test can keep about 95% of the specific capacity. In the presence of Li: ti: zn+(0.8-0.85): 1, (0.01-0.05) the preparation is carried out for a plurality of times in different proportions, and the cycle performance and the rate performance are not obviously different from those of the example 1.
Comparative example 1 can be prepared to resemble a beaded fibrous structure material, but the cycling performance and rate capability are poor, as shown in fig. 4, 5. The discharge capacity at the rate of 1C is 128mAh/g, and the capacity after 50 times of circulation is 111 mAh/g. And then, carrying out rate performance tests on the button battery with stable performance under the conditions of 0.5C, 1C, 2C and 3C, wherein the specific capacity is 112mAh/g, 100mAh/g, 89mAh/g and 72mAh/g in sequence.
Comparative example 2 zinc acetate was replaced with zinc nitrate, and the particle morphology thereof is shown in fig. 6, which does not form a chain-like fiber structure, and the cycle performance and rate performance thereof are shown in fig. 7 and fig. 8, the discharge capacity at 1C rate was 140mAh/g, and the capacity after 50 cycles was 137 mAh/g. And then, carrying out rate performance tests on the button cell with stable performance under the conditions of 0.5C, 1C, 2C and 3C, wherein the specific capacities are 125mAh/g, 112mAh/g, 104mAh/g and 85mAh/g in sequence, and compared with the button cell with stable performance, the button cell with stable performance is obviously poor in cycle performance and rate performance, but is improved to a certain extent compared with the button cell with stable performance in comparative example 1.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A chain-like fiber structure lithium titanate compound is characterized by comprising a lithium source material, a titanium source material and zinc acetate.
2. The composite of claim 1, wherein the lithium source material, the titanium source material, and the zinc acetate are in terms of Li, Ti, and Zn molar ratios, Li: ti: zn+＝(0.8-0.85)：1:(0.01-0.05)。
3. The composite of claim 2, wherein the lithium source material, the titanium source material, and the zinc acetate are in terms of Li, Ti, and Zn molar ratios, Li: ti: zn+＝0.82：1：0.01。
4. The composite according to any one of claims 1 to 3, wherein the lithium source material is one or more of lithium acetate, lithium hydroxide and lithium carbonate; the titanium source material is one or more than two of tetrabutyl titanate, titanium tetrachloride and n-propyl titanate.
5. Use of a composite according to any one of claims 1 to 4 in the manufacture of a lithium battery.
6. A lithium battery comprising the composite according to any one of claims 1 to 4 as an electrode active material.
7. A method for preparing a complex as claimed in any one of claims 1 to 4, comprising:
step 1, preparing an electrostatic spinning solution containing a lithium source material, a titanium source material, zinc acetate, an organic solvent and a dispersing agent;
step 2, preparing a lithium titanate compound precursor by electrostatic spinning;
and 3, calcining the lithium titanate compound precursor at high temperature to obtain the compound.
8. The method according to claim 7, wherein the step 1 is:
dissolving a titanium source material in glacial acetic acid to prepare a titanium source solution; dissolving an organic solvent in a dispersing agent to obtain an organic solvent solution, pouring a titanium source solution into the organic solvent solution, stirring, adding a lithium source material and zinc acetate, and continuing stirring until a transparent sol-gel solution, namely the electrostatic spinning solution, is obtained.
9. The method according to claim 7 or 8, wherein the organic solvent is polyvinylpyrrolidone, and the dispersant is ethanol and/or acetone.
10. The preparation method of claim 7, wherein the high-temperature calcination in the step 3 is calcination at 700-900 ℃ for 1-2 h.
CN202111501179.5A 2021-12-09 2021-12-09 Chain-like fiber structure lithium titanate compound and preparation method and application thereof Pending CN114388752A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115036489A (en) * 2022-06-27 2022-09-09 电子科技大学 Preparation method of high-safety lithium storage material based on lithium titanate heterostructure

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115036489A (en) * 2022-06-27 2022-09-09 电子科技大学 Preparation method of high-safety lithium storage material based on lithium titanate heterostructure
CN115036489B (en) * 2022-06-27 2023-11-17 电子科技大学 Preparation method of lithium storage material based on lithium titanate heterostructure

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