CN110707294B - Lithium-philic heteroatom and metal oxide co-doped three-dimensional fiber framework lithium battery cathode and preparation method thereof - Google Patents
Lithium-philic heteroatom and metal oxide co-doped three-dimensional fiber framework lithium battery cathode and preparation method thereof Download PDFInfo
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- CN110707294B CN110707294B CN201910810559.3A CN201910810559A CN110707294B CN 110707294 B CN110707294 B CN 110707294B CN 201910810559 A CN201910810559 A CN 201910810559A CN 110707294 B CN110707294 B CN 110707294B
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H—ELECTRICITY
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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
- H01M10/052—Li-accumulators
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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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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
A three-dimensional fiber frame lithium battery cathode codoped by lithium-philic heteroatoms and metal oxides and a preparation method thereof belong to the technical field of lithium battery cathodes. The preparation method comprises the following steps: synthesizing zinc hydroxide in a gelatin solution to form a uniformly dispersed suspension; spinning the suspension on the surface of a copper foil by using an electrostatic spinning technology to form an electrostatic spinning fiber film, and standing at room temperature to volatilize the solvent to form the copper foil with the gelatin spinning film; heating to convert zinc hydroxide into zinc oxide; assembling the modified copper foil and a lithium metal sheet into a button battery, standing for 10 hours, and depositing lithium metal on the modified copper foil by using an electrochemical deposition method; and disassembling the button battery and taking out the copper foil to obtain the required lithium metal cathode. The problems of generation and growth of lithium dendrites in the battery cycle process of the lithium negative electrode are solved, and the lithium negative electrode has excellent cycle stability.
Description
Technical Field
The invention relates to a design and preparation method of a three-dimensional fiber frame lithium battery cathode codoped by a lithium-philic heteroatom and a metal oxide and an obtained lithium cathode, belonging to the field of energy storage devices and energy materials.
Background
The new renewable energy, such as the utilization of hydroenergy, solar energy etc., the gradual marketization of electric automobile etc., the rapid development of various portable equipment all needs high-efficient practical energy storage and transportation system, but to new-type "green" energy storage device, when cutting its "green", can decide whether its key that is fit for the industrial application is whether it has important index such as high power density, high energy density. New power systems, particularly secondary batteries, are currently important "green" energy storage devices.
Since the first launch in the 90 s of the 20 th century, lithium ion batteries, one of the mainstream products in the portable device market, have been known for more than 20 years and are one of the most common rechargeable power sources, and lithium metal has high electronegativity and the lowest density among all metals, and therefore has the highest specific capacity (3861mA h g)-1) And is considered to be the best negative electrode of the rechargeable battery. However, the lithium negative electrode has a serious problem in the using process, namely the generation and growth of lithium dendrite, on one hand, the lithium dendrite can be separated from the negative electrode and enter into electrolyte to form 'dead lithium' when growing to a certain extent, so that the utilization rate of the metal of the negative electrode is reduced, and on the other hand, when the lithium dendrite grows to a certain extent, the lithium dendrite can be separated from the negative electrode to form 'dead lithium' inWhen the size is large, the diaphragm is easy to pierce, so that the anode and the cathode of the battery are in contact, the battery is short-circuited, and the safety problem is caused. The generation and development of lithium dendrites seriously hinder the long cycle stability of lithium batteries, the safety of batteries, and the like, and therefore, the development of a stable and safe negative electrode of lithium batteries is urgently needed to promote the development of the lithium battery industry.
A transition metal oxide comprising: fe2O3,ZnO,Mn3O4,NiCo2O4And CoFe2O4The lithium ion battery has high theoretical capacity and good lithium affinity, and has good application prospect in the negative electrode of the lithium battery.
Gelatin is a natural polymer material and is formed by degrading collagen parts in connective tissues such as animal skins, bones and the like, so the structure of the gelatin is similar to that of biological tissues, the gelatin mainly comprises more than 80 percent of protein, and the balance of water and inorganic salt, has good dispersibility, cohesiveness and the like, utilizes the polymer characteristics of the gelatin and is applied to the manufacture of batteries under the current trend of pursuing environmental protection and green chemistry, and has good application prospect.
Disclosure of Invention
In order to better meet the requirements of social development on stable and safe secondary rechargeable lithium batteries, the invention provides a design and preparation method of a lithium heteroatom and metal oxide co-doped three-dimensional fiber frame lithium battery cathode and the obtained lithium cathode, so as to solve the problems of generation and growth of lithium dendrites in the battery cycle process of the lithium cathode.
The preparation method of the lithium negative electrode provided by the invention comprises the following steps:
(1) in-situ reacting zinc acetate dihydrate with lithium hydroxide monohydrate in a gelatin solution to synthesize zinc hydroxide to form uniformly dispersed suspension;
(2) spinning the suspension on the surface of a copper foil by using an electrostatic spinning technology to form an electrostatic spinning fiber film, and standing at room temperature to volatilize the solvent to form the copper foil with the gelatin spinning film;
(3) heating the copper foil with the gelatin spinning film at 180 ℃ to convert zinc hydroxide into zinc oxide;
(4) assembling the modified copper foil and a lithium metal sheet into a button battery, standing for 10 hours, and depositing lithium metal on the modified copper foil by using an electrochemical deposition method;
(5) and disassembling the button battery and taking out the copper foil to obtain the required lithium metal cathode.
Further, in the step (1), the reaction of zinc acetate dihydrate and lithium hydroxide monohydrate is as follows:
Zn(CH3COO)2·2H2O+2LiOH·H2O→Zn(OH)2+2Li(CH3COO)+4H2O
the mass concentration of the gelatin solution prepared in the step (1) is preferably 8-15 wt%.
In the step (1), the solvent of the gelatin solution is prepared by mixing water and trifluoroethanol in a mass ratio of 1:1 under the condition of the formula (I).
The molar ratio of zinc acetate dihydrate to lithium hydroxide monohydrate is 1: 2. so that the final Zn (OH)2The concentration of (B) is 0.1 wt% to 1 wt%.
In the step (2), a gelatin fiber film containing zinc hydroxide (film thickness of 0.01-0.05mm, preferably 0.02mm) is prepared by an electrospinning technique and is attached to the surface of the copper foil.
Further, in the step (3), the zinc hydroxide is converted into zinc oxide through the following reaction:
Zn(OH)2→ZnO+H2O
further preferably, after the zinc hydroxide obtained by the reaction in the step (1) is dehydrated by heating in the step (3) to obtain zinc oxide, the mass fraction of zinc oxide/(zinc oxide + gelatin) is 1.25%.
And (4) heating the copper foil with the gelatin electrostatic spinning film in the step (3) in a tube furnace filled with nitrogen.
The temperature range of the heating process in the step (3) is from room temperature to 180 ℃, the heating rate is 2 ℃/min, the heat preservation time at 180 ℃ is 5 hours, and the temperature is naturally reduced to 50 ℃ after heat preservation.
Further, the battery electrolyte used in step (4) is a common commercial lithium battery electrolyte, wherein the electrolyte solvent is DOL/DME1:1 (volume ratio) of solute containing 1M LiPF6And 0.4M LiNO3。
Further, the button cell assembled in the step (4) has a standing time of 10 hours.
The electrochemical deposition step in the step (4) is carried out at a current density of 0.2mA/cm2Depositing for 15-30 hours under the condition.
The invention also discloses the lithium negative plate prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
the main material gelatin used in the invention is natural biopolymer, which has good physical and chemical properties such as dispersibility, cohesiveness and processability, and can uniformly disperse zinc oxide and the electrostatic spinning film can be well adhered to the surface.
Abundant nitrogen atoms in the gelatin and uniformly dispersed zinc oxide have synergistic effect, and the three-dimensional structure of the electrostatic spinning film enables lithium to be uniformly deposited on the copper foil, so that the generation of lithium dendrites in the battery circulation process can be effectively avoided, and the long-cycle stability and the safety of the lithium battery are improved.
Drawings
FIG. 1 is a graph comparing the cycle performance of a lithium-on-battery consisting of a lithium negative electrode prepared in example 1 of the present invention with that of a conventional lithium-on-battery
Detailed Description
The present invention is further described with reference to the following specific examples, but the scope of the present invention is not limited thereto, and any changes or modifications made thereto should be construed as being within the scope of the present invention.
The battery separator used in the examples was a common commercial separator, Celgard 2325.
Example 1
(1) Preparation of stable and safe lithium cathode
Accurately weighing 5.0g of gelatin, fully dissolving the gelatin in 45.0g of solvent (wherein the mass ratio of water to trifluoroethanol is 1: 1), then evenly dividing the solvent into two parts, adding 0.356g of zinc acetate dihydrate into one part, adding 0.136g of lithium hydroxide monohydrate into the other part, uniformly stirring, dropwise adding the solution containing the lithium hydroxide monohydrate into the solution containing the zinc acetate dihydrate while stirring, reacting for half an hour in total, then spinning the solution into a fiber film (the film thickness is 0.02mm) on a copper foil by using an electrostatic spinning machine, and using the electrostatic spinning technical parameters in the step (2) as follows: the propelling quantity is 0.01mL/min, and the translation speed is 0.08 cm/min. It was allowed to stand at room temperature for 24 hours.
And heating the modified copper foil in a tube furnace filled with nitrogen, wherein the temperature range of the heating process is from room temperature to 180 ℃, the heating rate is 2 ℃/min, the heat preservation time at 180 ℃ is 5 hours, naturally cooling to 50 ℃ after heat preservation, taking out the material, and cutting the material into small wafers with the diameter of 12mm by using a cutting machine.
Assembling the round sheet and a common metal lithium sheet into a CR2025 type button cell in a glove box, wherein a diaphragm is Celgard 2325, and an electrolyte is DOL/DME (volume ratio) +1M LiPF6+0.4M LiNO3The assembled battery was left to stand for 10 hours.
The cell was operated at a current density of 0.2mA/cm2Discharging for 25 hours under the condition to realize the deposition of lithium on the modified copper foil, and taking out the copper foil with the deposited lithium to obtain the lithium negative electrode.
(2) Preparation of lithium pair cell
Assembling two lithium cathodes prepared by the steps into a CR2025 button cell in a glove box, wherein a diaphragm is Celgard 2325, and an electrolyte is DOL/DME (volume ratio) 1: 1) +1M LiPF6+0.4M LiNO3The assembled battery was left to stand for 10 hours.
Likewise, two pieces of common lithium metal were assembled into a lithium-pair battery as a control.
(3) Electrochemical performance testing of lithium on batteries
The cycle performance test is carried out on the lithium battery on the charging and discharging equipment, and the test conditions are as follows: the charging and discharging current density is 1.0mA/cm2And the charge and discharge amount is 1.0mAh/cm2. The results of the two cycle performance tests are shown in FIG. 1. As can be seen from the data in the figure, lithium-pair batteries assembled using lithium cathodes prepared according to the invention have smaller polarization voltages and are longer and longerThe stable cycle period shows that the preparation method of the lithium negative electrode and the obtained lithium negative electrode are feasible.
Those skilled in the art will recognize that a wide variety of modifications, alterations, and combinations can be made with respect to the above described embodiments without departing from the scope of the invention, and that such modifications, alterations, and combinations are to be viewed as being within the ambit of the inventive concept.
Claims (11)
1. A preparation method of a three-dimensional fiber framework lithium battery cathode codoped with lithium-philic heteroatoms and metal oxides is characterized by comprising the following steps:
(1) in-situ reacting zinc acetate dihydrate with lithium hydroxide monohydrate in a gelatin solution to synthesize zinc hydroxide to form uniformly dispersed suspension;
(2) spinning the suspension on the surface of a copper foil by using an electrostatic spinning technology to form an electrostatic spinning fiber film, and standing at room temperature to volatilize the solvent to form the copper foil with the gelatin spinning film;
(3) heating the copper foil with the gelatin spinning film at 180 ℃ to convert zinc hydroxide into zinc oxide;
(4) assembling the modified copper foil and a lithium metal sheet into a button battery, standing for 10 hours, and depositing lithium metal on the modified copper foil by using an electrochemical deposition method;
(5) and disassembling the button battery and taking out the copper foil to obtain the required lithium metal cathode.
2. The process according to claim 1, wherein the gelatin solution of step (1) has a mass concentration of 8 to 15 wt%.
3. The process according to claim 1, wherein in the step (1), the solvent of the gelatin solution is prepared from water and trifluoroethanol in a mass ratio of 1:1 under the condition of the formula (I).
4. The process according to claim 1, wherein the zinc acetate dihydrate and the oxyhydrogen monohydrateMolar ratio of lithium compound 1: 2; so that the final Zn (OH)2The concentration of (B) is 0.1 wt% to 1 wt%.
5. The method of claim 1, wherein the gelatin fiber film containing zinc hydroxide is prepared in step (2) by an electrospinning technique to have a film thickness of 0.01 to 0.05mm and attached to the surface of the copper foil.
6. The production method according to claim 1, wherein the film thickness is 0.02 mm.
7. The production method according to claim 1, wherein the mass ratio of zinc oxide/(zinc oxide + gelatin) after the zinc hydroxide obtained by the reaction in step (1) is dehydrated by heating in step (3) to obtain zinc oxide is 1.25%.
8. The production method according to claim 1, wherein the copper foil with the gelatin electrostatic spinning film in step (3) is heated in a tube furnace filled with nitrogen gas; the temperature range of the heating process in the step (3) is from room temperature to 180 ℃, the heating rate is 2 ℃/min, the heat preservation time at 180 ℃ is 5 hours, and the temperature is naturally reduced to 50 ℃ after heat preservation.
9. The method of claim 1, wherein the battery electrolyte used in step (4) is a common commercial lithium battery electrolyte having a DOL/DME volume ratio of 1:1 and containing a solute of 1M LiPF6And 0.4M LiNO3。
10. The production method according to claim 1, wherein the electrochemical deposition step in the step (4) is carried out at a current density of 0.2mA/cm2Depositing for 15-30 hours under the condition.
11. The lithium-philic heteroatom and metal oxide co-doped three-dimensional fiber framework lithium battery negative electrode prepared by the method of any one of claims 1 to 10.
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| CN111952543B (en) * | 2020-08-24 | 2023-05-05 | 广东工业大学 | Three-dimensional lithium metal electrode, preparation method thereof and lithium metal battery |
| CN111864186B (en) * | 2020-08-27 | 2021-09-21 | 中南大学 | Preparation method of three-dimensional porous metal lithium anode |
| CN112216811A (en) * | 2020-09-23 | 2021-01-12 | 电子科技大学 | Preparation method of ultrathin lithium metal cathode |
| WO2022205107A1 (en) * | 2021-03-31 | 2022-10-06 | 宁德新能源科技有限公司 | Negative electrode pole piece, electrochemical device, and electronic device |
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| CN103165893A (en) * | 2011-12-15 | 2013-06-19 | 江南大学 | Preparation method of zinc oxide nanometer fiber cathode material for lithium ion battery |
| CN104562438B (en) * | 2013-10-17 | 2017-07-14 | 中国科学院理化技术研究所 | Gelatin-based micro nanometer fiber membrane material and its production and use |
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