CN113629231B - Magnetically induced cobalt fiber/metallic lithium composite electrode material, and preparation method and application thereof - Google Patents
Magnetically induced cobalt fiber/metallic lithium composite electrode material, and preparation method and application thereof Download PDFInfo
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- CN113629231B CN113629231B CN202110901004.7A CN202110901004A CN113629231B CN 113629231 B CN113629231 B CN 113629231B CN 202110901004 A CN202110901004 A CN 202110901004A CN 113629231 B CN113629231 B CN 113629231B
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- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
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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
The invention discloses a cobalt fiber/metallic lithium composite electrode material grown by magnetic induction, a preparation method and application thereof. The cobalt fiber/metal lithium composite electrode material can effectively slow-release volume change in the metal lithium deposition process, remarkably disperse and reduce reactive current density, promote electric field distribution uniformity in the metal lithium deposition process and inhibit dendrite growth, has higher high-cycle stability, rate capability and coulomb efficiency, can effectively improve electrochemical performance of a lithium metal battery, and has wide application prospects in the fields of mobile communication, electric automobiles, solar power generation, aerospace and the like.
Description
Technical Field
The invention relates to the technical field of lithium metal composite anode materials, in particular to preparation of a composite electrode material of cobalt fibers and metallic lithium which are magnetically induced to grow and application of the composite electrode material in a lithium metal anode.
Background
In recent years, lithium ion batteries have been widely used as energy storage devices in various large electronic devices. However, the theoretical capacity and the energy density of the lithium ion battery are low, and the requirements of people on the battery with high specific capacity and high energy density cannot be met. Metallic lithium with the highest theoretical capacity (3860 mAh/g), the lowest electrochemical potential (-3.04V vs. standard hydrogen electrode) was thus generated. If the positive electrode matches sulfur, the energy density is more high than 2600Wh/kg. Therefore, lithium metal batteries have been attracting attention from researchers in recent years.
Although the inherent characteristics of lithium metal determine that lithium metal batteries have high energy densities, this presents a significant challenge for commercial applications of lithium metal batteries. Mainly in the following aspects. First, lithium dendrite formation and growth problems. In fact, non-uniform deposition of metal ions is common among many metals, such as lithium, zinc, copper, nickel, silver, and the like. The non-uniform deposition characteristics of the metal ions enable the metal to be depositedDendritic morphology is formed in the process. For lithium metal batteries, li repeatedly occurs during the charge and discharge processes + So that needle-like projections, so-called "dendrites", are formed on the surface of the metallic lithium. These dendrites will puncture the separator and cause internal shorting of the cell, causing thermal failure of the cell and in severe cases, more likely to cause spontaneous ignition and explosion of the cell. Second, there is a large volume change during deposition. Throughout the lithium ion battery, various negative electrode materials have certain volume changes. For example, the volume change of a commercial graphite anode is about 10% when lithium ions are intercalated, the volume change of a silicon anode is 400% in the lithiation process, and the volume change of lithium metal is infinite in theory. The SEI film formed on the surface in situ is often broken due to larger volume change in the metal lithium deposition process, so that on one hand, a new lithium source is promoted to react with electrolyte, and the coulomb efficiency of the battery is reduced; on the other hand, the crack is often an active site area, which induces the generation of lithium dendrites, resulting in a short cycle life of the battery. Third, the interface is unstable. The lithium having the lowest electrochemical potential means that metallic lithium has strong reducing activity and easily loses the outer electrons to form Li + . Studies have shown that metallic lithium can react with almost all electrolytes. After the metal lithium reacts with the electrolyte, a SEI film is formed on the surface of the lithium in situ, so that further reaction between the metal lithium and the electrolyte is inhibited. However, the SEI film formed in situ tends to be nonuniform in composition and distribution, and Li cannot be induced + Is deposited uniformly; the poor mechanical properties make SEI films unable to bear the stress generated by the larger volume change in the repeated deposition/shedding process of lithium, which causes SEI film rupture and unstable interface.
In view of the above problems with lithium metal, the current solutions mainly include the following: (1) After the three-dimensional network skeleton is introduced and compounded with lithium metal, the local current density on the surface of the electrode can be effectively reduced, and the volume expansion is relieved to a certain extent; (2) SEI modification: by introducing an artificial SEI film on the surface of lithium metal, the flow of lithium ions on the surface of an electrode is homogenized, and stable deposition of metal lithium is realized; (3) electrolyte modification: by adding other effective components into the electrolyte, a more stable SEI film is formed in situ; (4) introducing a solid electrolyte. Compared with liquid organic electrolyte, the solid electrolyte is nonflammable and has good mechanical property, can physically inhibit the growth of lithium dendrite, and improves the safety of the battery. The first scheme is widely applied, the composite three-dimensional porous conductive carrier can be used for remarkably dispersing and reducing the reaction current density at an interface, improving the electric field distribution uniformity in the metal lithium deposition process and inhibiting dendrite growth, so that the electrochemical performance is effectively improved.
Disclosure of Invention
The invention aims at solving the problems of volume expansion, dendrite growth and the like of a lithium metal anode, and provides a preparation method of magnetically induced growth cobalt fibers.
The cobalt fiber with the extremely large length-diameter ratio and specific surface area is prepared in a magnetic induction mode, is used as a substrate of the lithium metal anode, effectively relieves the volume effect in the lithium deposition process and inhibits the growth of lithium dendrites, and is a novel and effective substrate material. So far, no report on magnetically induced growth of metal fiber materials exists, and therefore, the method has great exploratory value.
The preparation method of the magnetically induced cobalt fiber/metallic lithium composite electrode material comprises the following steps:
(1) Cobalt acetate tetrahydrate is used as solute and water is used as solvent to prepare cobalt acetate aqueous solution;
(2) Adding hydrazine hydrate into the solution, and magnetically stirring to obtain a reaction solution;
(3) Sequentially placing the magnet and the substrate material into a hydrothermal liner, pouring the hydrothermal reaction solution, and performing hydrothermal reaction at 150-300 ℃ for 6-12 h to obtain a hydrothermal reaction product;
(4) Taking out the hydrothermal reaction product, washing with water, and freeze-drying for 12-24 hours to obtain a substrate material for growing cobalt fibers;
(5) And compounding the metal lithium with the cobalt fiber in a molten lithium mode to obtain the cobalt fiber/metal lithium composite material.
The following is a preferred technical solution of the present invention:
in the step (1), the concentration of the aqueous solution of cobalt acetate is 0.05mol/L to 0.5mol/L, and more preferably, the solubility of the aqueous solution of cobalt acetate is 0.05mol/L to 0.2mol/L.
In the step (2), the ratio of the amount (mol) of the cobalt acetate tetrahydrate substance to the volume (L) of the hydrazine hydrate is 0.5-2:1, and more preferably 0.5-1: 1, the magnetic stirring is carried out for 10 min-30 min (preferably 15 min).
In the step (3), the base material is cobalt sheet, foam nickel, nickel sheet, polytetrafluoroethylene plate and the like, the magnet is round, the base material is round, the magnet base material needs to be cleaned before use, the base material (cobalt sheet, foam nickel, nickel sheet, polytetrafluoroethylene plate and the like) is cut into circular sheets with a certain radius, and hydrochloric acid and deionized water are respectively used for ultrasonic cleaning for 30min.
In the step (3), the hydrothermal reaction temperature is 200-300 ℃; the hydrothermal reaction time is 9-10 h.
In the step (4), deionized water is used for washing 3 to 5 times.
In step (5), the mode of melting lithium specifically includes: adding a lithium sheet on a heating table, regulating the temperature to 200-500 ℃ for 20-40 min to obtain molten metal lithium, and putting a substrate material for growing cobalt fibers into the substrate material for soaking for 5-10min to obtain the cobalt fiber/metal lithium composite electrode material.
The cobalt fiber prepared by magnetic induction has larger specific surface area, can relieve volume change in the metal lithium deposition process, and the vertically grown cobalt fiber can reduce the curvature in the lithium ion diffusion process, can be used as a lithium metal anode material, and is more suitable for being used as an anode substrate material of a lithium metal battery.
Compared with the prior art, the invention has the following advantages:
the magnetically induced hydrothermally grown cobalt fiber is a novel substrate material, and the cobalt fiber vertically grows on various substrate materials under the induction of a magnetic field, including cobalt sheets, foam nickel, nickel sheets and the like. The magnetically induced cobalt fiber is formed by a single particleCobalt particles with diameters of 4-5 mu m are directionally stacked, and the length can be regulated and controlled from micron level to centimeter level by regulating the amount of the precursor. There are a large number of voids between the directionally grown cobalt fibers. BET test shows that the specific surface area of the cobalt fiber is 12.083m 2 /g (carbon cloth 4.128 m) 2 /g; foam nickel of 2.227m 2 /g). The fiber preparation method is simple and easy to control. And the magnetic field induction is also a novel material preparation technology for preparing the metal fiber material.
The cobalt fiber electrode material prepared by the invention has larger specific surface area, can effectively increase the load capacity and active reaction area of metallic lithium, and simultaneously, the cobalt fiber which is magnetically induced to vertically grow is Li + And a diffusion channel is provided, so that the diffusion distance is shortened, and the reaction kinetics process is improved. After the cobalt fiber and the metal lithium are compounded, the composite anode improves the multiplying power performance and the cycle performance of the lithium metal battery, and is beneficial to the development of the lithium metal battery with high energy density and high stability.
The invention obtains directionally grown cobalt fibers on various substrate materials through magnetic induction hydrothermal reaction, and then prepares the cobalt fiber/metal lithium composite material by compounding through a molten lithium method. The cobalt fiber/metal lithium composite electrode material can effectively slow-release volume change in the metal lithium deposition process, remarkably disperse and reduce reactive current density, promote electric field distribution uniformity in the metal lithium deposition process and inhibit dendrite growth, has higher high-cycle stability, rate capability and coulomb efficiency, can effectively improve electrochemical performance of a lithium metal battery, and has wide application prospects in the fields of mobile communication, electric automobiles, solar power generation, aerospace and the like.
Drawings
FIG. 1 is a schematic diagram of example 1;
FIGS. 2 and 3 are cobalt fiber scanning electron microscope images at different magnifications in example 1;
FIG. 4 is a cross-sectional scanning electron microscope image of magnetically induced cobalt fibers vertically grown on nickel foam in example 1;
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
Example 1
Co (AC) 1.495g 2 ·4H 2 O was added to 70ml of deionized water and stirred at room temperature of 25℃for 30 minutes to give a reddish transparent solution (cobalt acetate solution 0.085 mol/L). Subsequently to configured Co (AC) 2 6ml of N was added to the aqueous solution 2 H 4 ·H 2 O and stirred for 15min. And respectively ultrasonically cleaning the substrate material foam nickel by hydrochloric acid and deionized water for 30min, pouring the obtained solution into a hydrothermal reaction kettle in which a magnet and foam nickel are placed, and placing the hydrothermal reaction kettle in an oven at 200 ℃ for reaction for 10h. After the reaction was completed, the base material was taken out and washed 3 times with deionized water, followed by freeze-drying for 12 hours to obtain a cobalt fiber film. In an argon-filled glove box with oxygen content less than 0.1ppm and water content less than 0.1ppm, placing a nickel crucible on a heating table, adding a lithium sheet, adjusting the temperature of the heating table to 400 ℃ for 30min to obtain molten metal lithium, and placing a cobalt fiber base material into the nickel crucible for soaking for 8min to obtain the cobalt fiber/metal lithium composite electrode material.
Example 2
Co (AC) 1.495g 2 ·4H 2 O was added to 70ml of deionized water and stirred at room temperature of 25℃for 30min to give a reddish transparent solution (0.085 mol/L). Subsequently to configured Co (AC) 2 6ml of N was added to the aqueous solution 2 H 4 ·H 2 O and stirred for 15min. And respectively ultrasonically cleaning the substrate material foam nickel by hydrochloric acid and deionized water for 30min, pouring the obtained solution into a hydrothermal reaction kettle in which a magnet and foam nickel are placed, and placing the hydrothermal reaction kettle in an oven at 240 ℃ for reaction for 10h. After the reaction was completed, the base material was taken out and washed 3 times with deionized water, followed by freeze-drying for 12 hours to obtain a cobalt fiber film. In an argon-filled glove box with oxygen content less than 0.1ppm and water content less than 0.1ppm, placing a nickel crucible on a heating table, adding a lithium sheet, adjusting the temperature of the heating table to 400 ℃ for 30min to obtain molten metal lithium, and placing a cobalt fiber base material into the nickel crucible for soaking for 10min to obtain the cobalt fiber/metal lithium composite electrode material.
Example 3
Co (AC) 1.495g 2 ·4H 2 O was added to 70ml of deionized water and stirred at room temperature of 25℃for 30min to give a reddish transparent solution (0.085 mol/L). Subsequently to configured Co (AC) 2 6ml of N was added to the aqueous solution 2 H 4 ·H 2 O and stirred for 15min. And respectively ultrasonically cleaning the substrate material foam nickel by hydrochloric acid and deionized water for 30min, pouring the obtained solution into a hydrothermal reaction kettle in which a magnet and foam nickel are placed, and placing the hydrothermal reaction kettle in an oven at 260 ℃ for reaction for 10h. After the reaction was completed, the base material was taken out and washed 3 times with deionized water, followed by freeze-drying for 12 hours to obtain a cobalt fiber film. In an argon-filled glove box with oxygen content less than 0.1ppm and water content less than 0.1ppm, placing a nickel crucible on a heating table, adding a lithium sheet, adjusting the temperature of the heating table to 400 ℃ for 30min to obtain molten metal lithium, and placing a cobalt fiber base material into the nickel crucible for soaking for 5min to obtain the cobalt fiber/metal lithium composite electrode material.
Performance testing
The cobalt/lithium composite electrode materials prepared in examples 1 to 3 were assembled into lithium-lithium symmetric batteries in an argon atmosphere glove box for electrochemical testing. The electrolyte is added with 1wt% LiNO 3 LiTFSI/DOL of 1 mol/L: DEM (1:1 volume ratio, DOL:1, 3-dioxolane; DME: ethylene glycol dimethyl ether), the diaphragm being of Celgard2400 type. And assembling the battery according to the sequence of the positive electrode shell, the cobalt/lithium composite electrode material, the electrolyte, the diaphragm, the cobalt/lithium composite electrode material and the negative electrode shell, and compacting and sealing by using a full-automatic packaging machine. After the cell was left to stand for 24 hours, electrochemical testing was performed using the new wire and electrochemical workstation. The electrochemical tests are all carried out at 25 ℃ and mainly comprise constant current charge and discharge tests and electrochemical impedance analysis. At a current density of 1mA/cm 2 The capacity is 1mAh/cm 2 The long cycle performance of the battery is tested under the condition of (1); at 0.5mA/cm 2 The specific capacity of the cobalt/lithium composite electrode material was tested at the current density of (c).
The performance test results are as follows:
the interface impedances of the lithium metal battery cobalt/lithium composite electrode materials of example 1, example 2 and example 3 before cycling are 50Ω, 30Ω and 35Ω, respectively; the interface impedance is reduced to 15 after 100h of circulationΩ, 10Ω, 14Ω. At 0.5mA/cm 2 The discharge specific capacities of the cobalt/lithium composite electrode materials are 3000mAh/g, 3115mAh/g and 3084mAh/g respectively, which indicates that the introduction of the inactive cobalt fiber skeleton does not obviously reduce the actual capacity of the materials. At 1mA/cm 2 Current density, 1mAh/cm 2 The lithium metal batteries of example 1, example 2 and example 3 were assembled with cobalt/lithium composite electrode materials having stable overpotential of 36mV, 30mV, 34mV, respectively, and the batteries did not appear short circuit after 900 hours of cycling. Therefore, the prepared cobalt/lithium composite electrode material of the lithium metal battery has high capacity and good cycle stability.
The introduction of cobalt fibers can relieve the volume change in the metal lithium deposition process, and the vertically oriented growth fibers can reduce the curvature of the lithium ion diffusion process and improve the reaction kinetics. Therefore, the cobalt fiber/lithium composite electrode material of the lithium metal battery has good cycle stability and rate capability, and has wide application prospects in the fields of small-sized mobile electronic equipment, electric automobiles, solar power generation, aerospace and the like.
Claims (8)
1. The preparation method of the cobalt fiber/lithium metal composite electrode material with magnetic induction vertical growth is characterized by comprising the following steps:
(1) Cobalt acetate tetrahydrate is used as solute and water is used as solvent to prepare cobalt acetate aqueous solution;
(2) Adding hydrazine hydrate into the solution, and magnetically stirring to obtain a reaction solution;
(3) Sequentially placing the magnet and the substrate material into a hydrothermal liner, pouring a reaction solution, and performing hydrothermal reaction at 150-300 ℃ for 6-12 hours to obtain a hydrothermal reaction product;
(4) Taking out a hydrothermal reaction product, washing with water, and freeze-drying for 12-24 hours to obtain a substrate material for vertically growing cobalt fibers;
the substrate material is cobalt sheet, foam nickel, nickel sheet or polytetrafluoroethylene plate;
(5) Compounding metal lithium and cobalt fiber in a molten lithium mode to obtain a cobalt fiber/metal lithium composite material;
the mode of melting lithium specifically includes: adding a lithium sheet on a heating table, adjusting the temperature of the heating table to 200-500 ℃ for 20-40 min to obtain molten metal lithium, and putting a substrate material for growing cobalt fibers into the substrate material for soaking for 5-10min to obtain the cobalt fiber/metal lithium composite electrode material.
2. The method for preparing the magnetically induced vertically grown cobalt fiber/lithium metal composite electrode material according to claim 1, wherein in the step (1), the concentration of the aqueous solution of cobalt acetate is 0.05mol/L to 0.5mol/L.
3. The method for preparing a magnetically induced vertically grown cobalt fiber/lithium metal composite electrode material according to claim 1, wherein in the step (2), the volume ratio of the amount of the cobalt acetate tetrahydrate substance to the hydrazine hydrate is 0.5 mol-2 mol:1L.
4. The method for preparing the magnetically induced vertically grown cobalt fiber/lithium metal composite electrode material according to claim 1, wherein in the step (2), the magnetic stirring time is 10-30 min.
5. The method for preparing a magnetically induced vertically grown cobalt fiber/lithium metal composite electrode material according to claim 1, wherein in the step (3), the magnet is circular, and the base material is circular.
6. The method for preparing the magnetically induced vertically grown cobalt fiber/lithium metal composite electrode material according to claim 1, wherein in the step (3), hydrothermal reaction is carried out at 200-300 ℃ for 9-10 h.
7. The method for preparing the cobalt fiber/lithium metal composite electrode material according to any one of claims 1-6.
8. Use of the cobalt fiber/lithium metal composite electrode material according to claim 7 as a lithium metal negative electrode material.
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| CN109261981A (en) * | 2018-08-20 | 2019-01-25 | 浙江师范大学 | Bimetallic cobalt-based core-shell material and the preparation method and application thereof |
| CN111599983A (en) * | 2020-05-18 | 2020-08-28 | 中山大学 | Lithium metal composite negative electrode with hydrophilic-hydrophobic lithium gradient structure and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109261981A (en) * | 2018-08-20 | 2019-01-25 | 浙江师范大学 | Bimetallic cobalt-based core-shell material and the preparation method and application thereof |
| CN111599983A (en) * | 2020-05-18 | 2020-08-28 | 中山大学 | Lithium metal composite negative electrode with hydrophilic-hydrophobic lithium gradient structure and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| Nitrogen-doped polymer nanofibers decorated with Co nanoparticles for uniform lithium nucleation/growth in lithium metal batteries;Miao Shu等;《Nanoscale》;20200512;第12卷;第8819-8827页 * |
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