CN111952543A - Three-dimensional lithium metal electrode, preparation method thereof and lithium metal battery - Google Patents
Three-dimensional lithium metal electrode, preparation method thereof and lithium metal battery Download PDFInfo
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Abstract
The application belongs to the technical field of lithium metal electrodes. The application provides a three-dimensional lithium metal electrode, a preparation method thereof and a lithium metal battery, wherein metal lithium is embedded into a three-dimensional porous support, so that local current density can be effectively reduced, lithium ion deposition is homogenized, growth of lithium dendrites is inhibited, and overpotential of lithium ion deposition is reduced. The three-dimensional porous support is composed of a precursor material and a metal foil, the precursor material and the metal foil are mutually permeated to form an anchoring structure, the volume change in the battery circulation process can be accommodated, the coulomb efficiency is further improved, and the safety of the lithium metal battery is greatly improved. In addition, the stable three-dimensional porous support with the anchoring structure is embedded with the metal lithium, so that the problem that the structure of the common three-dimensional support collapses easily in the reciprocating circulation process is effectively solved, the long-time structural stability can be kept, the long-time circulation performance of the battery can be realized, and the electrochemical performance of the lithium metal battery is improved.
Description
Technical Field
The application belongs to the technical field of lithium metal electrodes, and particularly relates to a three-dimensional lithium metal electrode, a preparation method of the three-dimensional lithium metal electrode and a lithium metal battery.
Background
The lithium metal has ultrahigh theoretical specific capacity (3860mAh g)-1) Lower bulk density (0.534g cm)-3) And the lowest reduction potential-3.04V (relative to a standard hydrogen electrode), are considered to be the most promising anode materials. However, in the electroplating/stripping process, the lithium metal foil is used as a lithium metal negative electrode, lithium ions tend to deposit at the convex position due to the lightning rod effect, so that lithium dendrites are gradually formed on the surface of the electrode, lithium dendrites are exposed in the electrolyte, and the lithium metal and the electrolyte are greatly consumed as the cycle number increases, and the dendrites continue to grow to form dead lithium. In addition, due to the host-free characteristic of lithium metal, the electrode has huge volume change in the circulating process, so that the circulating coulombic efficiency of the battery is reduced, even the battery explodes, and the practical application of the lithium metal cathode is seriously hindered.
In response to the above problems, Pathak et al eliminate lithium dendrites and dead lithium by creating an artificial SEI that is tightly fixed to the Li surface by LiF, Sn and Sn-Li alloys, store lithium by forming alloys and plate lithium on the lower portion of alloys to achieve the goal of suppressing dendrite growth. Kang et al prepared a uniform carboxylic acid protective interface organic layer with a thickness of 1 μm by in situ spontaneous reaction of carboxylic acid of 5 carbon atoms with Li, effectively limiting the deposition of Li and inhibiting the growth of dendrites. Although these technical means can suppress dendritic growth to some extent, they still cannot accommodate the large volume change of the host-free lithium metal negative electrode during charge-discharge cycles. In addition, the common three-dimensional framework easily causes the problem of structural collapse in the reciprocating circulation process, so that the circulation performance is poor.
Disclosure of Invention
In view of this, the present application provides a three-dimensional lithium metal negative electrode, a method for preparing the same, and a lithium metal battery, so that the lithium metal negative electrode can adapt to a huge volume change in an electroplating stripping process, can maintain a stable structure for a long time, and can improve electrochemical performance of the lithium metal battery.
A first aspect of the present application provides a three-dimensional lithium metal electrode comprising a three-dimensional porous scaffold and metallic lithium intercalated into the three-dimensional porous scaffold;
the three-dimensional porous scaffold comprises a precursor material and a metal foil.
Preferably, the precursor material is a perovskite material, and the metal foil is a copper foil.
Preferably, the precursor material is selected from (La)0.6Sr0.4)0.95Co0.2Fe0.8O3-Or Ba0.5Sr0.5Co0.2Fe0.8O3-Wherein 0 < 3.
Preferably, the preparation method of the precursor material comprises the following steps:
metal salt is added according to the molar ratio of (La: Sr): (Co: Fe) (0.6:0.4)0.95:(0.2:0.8)1Or (Ba: Sr): (Co: Fe) ═ 0.5:0.5:0.2:0.8 is added into the solvent, then the polymer matrix is added, and the mixture is mixed, so as to obtain the precursor material.
Preferably, the using amount ratio of the metal salt to the solvent is 1mmol (2-5) ml, and the mass ratio of the metal salt to the polymer matrix is 1 (4-8)%.
Preferably, the metal salt is selected from La (NO)3)2·6H2O、Ba(NO3)2、Sr(NO3)2、Co(NO3)2·6H2O and Fe (NO)3)3·9H2And O.
Preferably, the solvent is selected from the group consisting of N, N-Dimethylformamide (DMF), ethanol (CH)3CH2OH) or water (H)2O)；
The polymer matrix is selected from Polyacrylonitrile (PAN), polyvinylpyrrolidone (PVP), polyvinyl butyral (PVB) or polyvinyl alcohol (PVA).
In a second aspect, the present application provides a method for preparing a three-dimensional lithium metal electrode, comprising the steps of:
step a: carrying out electrostatic spinning on the precursor material to the metal foil, drying and sintering to obtain the three-dimensional porous support;
step b: and filling the lithium metal melted at high temperature into the three-dimensional porous support to obtain the three-dimensional lithium metal electrode.
Preferably, the voltage applied to the electrostatic spinning is 10-20kV, the drying temperature is 50-100 ℃, the sintering temperature is (800-1000) DEG C, and the sintering time is 3-5 h. More preferably, the voltage applied to the electrostatic spinning is 15kV, the drying temperature is 80 ℃, the sintering temperature is (800-1000) ° c, and the sintering time is 4 hours;
the temperature of the high-temperature melting is 200-400 ℃.
The third aspect of the present application provides a lithium metal battery, including the three-dimensional lithium metal electrode, a spring, a gasket, a separator, and an electrolyte.
Wherein the negative electrode of the lithium metal battery may be the three-dimensional lithium metal negative electrode, and the positive electrode may be LiFePO4、LixCoO2(x>0)、LiyMnO2(y>0)、LiNi0.5Mn1.5O4、Li2TiO3At least one of Li, Cu, the three-dimensional metallic lithium positive electrode, a metal oxide or a metal sulfide. The membrane may be selected from at least one of a GF membrane, a PE membrane, a PP/PE membrane, or a PP/PE/PP membrane. The electrolyte can be selected from ether electrolyte, the solvent of the electrolyte is one or a combination of more than two of 1, 3-Dioxolane (DOL), ethylene glycol dimethyl ether (DME) or diethylene glycol Dimethyl Ether (DEDM), and the lithium salt in the electrolyte is selected from LITFSI, LIFSI and LiCF3SO3And LiBF4Any one of the above.
In summary, the present application provides a three-dimensional lithium metal electrode, a method of manufacturing the same, and a lithium metal battery. In this application, pack in three-dimensional porous support through the embedding of metal lithium, can effectively reduce local current density, the deposit of homogenization lithium ion, and then restrain the growth of lithium dendrite, reduce lithium ion deposition overpotential. The three-dimensional porous support is composed of a precursor material and a metal foil, the precursor material and the metal foil are mutually permeated to form an anchoring structure, the volume change in the battery circulation process can be accommodated, the coulomb efficiency is further improved, and the safety of the lithium metal battery is greatly improved. In addition, the stable three-dimensional porous support with the anchoring structure is embedded with the metal lithium, so that the problem that the structure of the common three-dimensional support collapses easily in the reciprocating circulation process is effectively solved, the long-time structural stability can be kept, the long-time circulation performance of the battery can be realized, and the electrochemical performance of the lithium metal battery is improved.
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In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive exercise.
FIG. 1 is an SEM image of the surface of lithium metal after a half-cell cycle test using three-dimensional lithium metal as an electrode in example 1 of the present application;
FIG. 2 is an SEM image of a lithium metal surface after a half-cell cycle test using a copper foil as an electrode in comparative example 1 of the present application;
FIG. 3 is a graph comparing the cycle performance of the half cell of example 1 of the present application and the half cell of comparative example 1;
FIG. 4 is a graph comparing the cycle performance of a symmetrical cell of example 1 of the present application and a symmetrical cell of comparative example 1;
FIG. 5 is a graph showing the results of cycle performance of the half cell of comparative example 3 of the present application;
fig. 6 is a graph of cycle performance results for the symmetrical cell of comparative example 3 of the present application.
Detailed Description
In order to make the objects, features and advantages of the present application more obvious and understandable, the technical solutions in the embodiments of the present application are clearly and completely described, and it is obvious that the embodiments described below are only a part 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.
Example 1
(1) Preparation of three-dimensional lithium metal electrode
a. Adding 1mmol of La (NO)3)2·6H2O、(Sr(NO3)2、Co(NO3)2·6H2O and Fe (NO)3)3·9H2O is added into the mixture in a molar ratio of (La: Sr): (Co: Fe) ═ 0.6:0.4)0.95:(0.2:0.8)1Adding the amount of the metal nitrate into 3ml of DMF solvent, adding 5 weight parts of PAN, stirring overnight to completely dissolve the metal nitrate to obtain a precursor material;
b. and (3) filling the prepared precursor material into a plastic injector with a stainless steel needle, connecting the injector to a high-voltage power supply, and performing electrostatic spinning, wherein the carrier used for electrostatic spinning is a copper foil, the applied voltage is fixed at 15kV, and the distance from the stainless steel needle to the foamed copper foil is kept at 15 cm. After electrostatic spinning, drying the product at 80 ℃ overnight, then placing the product in a tubular furnace at 800 ℃ and sintering the product for 4 hours in Ar atmosphere to obtain a three-dimensional porous support;
c. and (3) embedding molten lithium metal into the three-dimensional support at 300 ℃, and cooling to room temperature to obtain the three-dimensional lithium metal cathode.
(2) Assembly of lithium metal batteries
a. Assembling a half cell by taking a lithium foil as a negative electrode, the prepared three-dimensional lithium metal as a positive electrode, a PP film as a diaphragm and 1MLiTFSI/(DOL + DME) as an electrolyte;
b. and (3) assembling the symmetrical battery by using the prepared three-dimensional lithium metal as a positive electrode and a negative electrode, a PP film as a diaphragm and 1MLiTFSI/(DOL + DME) as an electrolyte.
(3) Electrochemical performance test
a. At 1mAh/cm2Deposition capacity, 1mA/cm2Carrying out charge-discharge cycle test on the half cell in the step (2) by using the current density and the charging voltage of 1V;
b. at 1mAh/cm2Deposition capacity, 1mA/cm2Current density the charge-discharge cycle test was performed on the symmetric cell in step (2), and the results are shown in fig. 3, fig. 4, and table 1.
Example 2
(1) Preparation of three-dimensional lithium metal electrode
a. 1mmol of (Ba (NO)3)2、(Sr(NO3)2、Co(NO3)2·6H2O and Fe (NO)3)3·9H2Adding O into 5ml of DMF solvent according to the molar ratio of (Ba: Sr) to (Co: Fe) of 0.5:0.5:0.2:0.8, adding PAN with the weight fraction of 8%, and stirring overnight to completely dissolve the metal nitrate to obtain a precursor material;
b. and (3) filling the prepared precursor material into a plastic injector with a stainless steel needle, connecting the injector to a high-voltage power supply, and performing electrostatic spinning, wherein the carrier used for electrostatic spinning is a copper foil, the applied voltage is fixed at 15kV, and the distance from the stainless steel needle to the foamed copper foil is kept at 15 cm. After electrostatic spinning, drying the product at 80 ℃ overnight, then placing the product in a tubular furnace at 850 ℃ and sintering the product for 4 hours in Ar atmosphere to obtain a three-dimensional porous support;
c. and (3) embedding molten lithium metal into the three-dimensional support at 350 ℃, and cooling to room temperature to obtain the three-dimensional lithium metal electrode.
(2) Assembly of lithium metal batteries
a. Assembling a half cell by taking a lithium foil as a negative electrode, the prepared three-dimensional lithium metal as a positive electrode, a PE film as a diaphragm and 1MLiFSI/(DOL + DME) as an electrolyte;
b. and (3) assembling the symmetrical battery by using the prepared three-dimensional lithium metal as a positive electrode and a negative electrode, a PE film as a diaphragm and 1MLiFSI/(DOL + DME) as an electrolyte.
(3) Electrochemical performance test
a. At 1mAh/cm2Deposition capacity, 0.5mA/cm2Current Density, 1V Charge Voltage Pair step(2) Carrying out charge-discharge cycle test on the half cell;
b. at 1mAh/cm2Deposition capacity, 0.5mA/cm2The current density was measured for the charge-discharge cycle of the symmetrical battery D in step (2), and the results are shown in table 1.
Comparative example 1
Assembling a half cell by taking a lithium foil as a negative electrode, a Cu foil as a positive electrode, a PP film as a diaphragm and 1M LiTFSI/(DOL + DME) as an electrolyte; and (3) assembling the symmetrical battery by using lithium foils as a positive electrode and a negative electrode, a PP film as a diaphragm and 1MLiTFSI/(DOL + DME) as an electrolyte.
At 1mAh/cm2Deposition capacity, 1mA/cm2Carrying out charge-discharge cycle test on the half-cell at the current density and the charging voltage of 1V; at 1mAh/cm2Deposition capacity, 1mA/cm2Current density charge and discharge cycling tests were performed on the symmetric cells and the results are shown in fig. 3, fig. 4 and table 1.
Comparative example 2
Assembling a half cell by taking a lithium foil as a negative electrode, a Cu foil as a positive electrode, a PE film as a diaphragm and 1M LiFSI/(DOL + DEDM) as an electrolyte; and (3) assembling the symmetrical battery by using lithium foils as a positive electrode and a negative electrode, using a PE film as a diaphragm and using 1M LiFSI/(DOL + DEDM) as an electrolyte.
At 1mAh/cm2Deposition capacity, 0.5mA/cm2Carrying out charge-discharge cycle test on the half-cell at the current density and the charging voltage of 1V; at 1mAh/cm2Deposition capacity, 0.5mA/cm2Current density charge and discharge cycling tests were performed on the symmetric cells and the results are shown in table 1.
Comparative example 3
Assembling a half cell by taking lithium foil as a negative electrode, taking lithium metal embedded in metal copper foam as a positive electrode, taking a PP film as a diaphragm and taking 1MLiTFSI/(DOL + DME) as electrolyte; lithium metal embedded in the metal copper foam is used as a positive electrode and a negative electrode, a PP film is used as a diaphragm, and 1M LiTFSI/(DOL + DME) is used as electrolyte to assemble the symmetrical battery.
At 1mAh/cm2Deposition capacity, 1mA/cm2Carrying out charge-discharge cycle test on the half-cell at the current density and the charging voltage of 1V; at 1mAh/cm2Deposition capacity, 1mA/cm2Current density charge-discharge cycling of symmetric batteriesThe results of the tests are shown in fig. 5, fig. 6 and table 1.
TABLE 1 results of the charge-discharge cycle test of the batteries of examples 1-2 and comparative examples 1-3
| Experimental number | Cycle life (h) | Coulombic efficiency (%) |
| Example 1 | 300 | 94 |
| Example 2 | 350 | 92 |
| Comparative example 1 | 157 | Instability of the film |
| Comparative example 2 | 120 | Instability of the film |
| Comparative example 3 | 250 | 89 |
The half-cells of example 1 and comparative example 1 after cycling were disassembled and characterized using a scanning electron microscope, and the results are shown in fig. 1 and 2. Comparing fig. 1 and fig. 2, it can be seen that the surface of the battery electrode assembled by the three-dimensional lithium metal electrode is flat, no lithium dendrite appears, while the dendrite on the surface of the battery electrode assembled by the common Cu foil grows willingly, which shows that the three-dimensional lithium metal electrode effectively inhibits the formation of the lithium dendrite.
As can be seen from the comparison graph of the cycle performance of the half cell assembled by respectively using the three-dimensional lithium metal electrode of example 1 and the copper foil of comparative example 1 as the electrode in fig. 3, the half cell using the three-dimensional lithium metal can be stably cycled for 100 cycles with the coulombic efficiency higher than 94%, while the half cell using the common Cu foil is rapidly attenuated after 50 cycles, which indicates that the coulombic efficiency of the cell is significantly improved by using the three-dimensional lithium metal electrode of the present application.
As can be seen from the comparison of the cycle performance of the symmetric Li battery assembled by using the three-dimensional lithium metal electrode in example 1 and the symmetric Li battery assembled by using the lithium foil as the electrode in comparative example 1 in fig. 4, the symmetric Li battery using the three-dimensional lithium metal electrode can stably cycle for more than 300 hours at a low overpotential of 55 mV; however, the overpotential of the symmetrical battery assembled by the lithium foil is large and the violent floating occurs, which shows that the three-dimensional lithium metal electrode reduces the deposition overpotential of lithium ions and improves the cycle stability of the lithium battery.
Comparing fig. 3 and 5, fig. 4 and 6, and the experimental results in table 1, it can be seen that the three-dimensional lithium metal electrode formed by embedding lithium metal into the three-dimensional porous scaffold of the present application has better cycle life and coulombic efficiency, and improves the electrochemical performance of the lithium battery to a certain extent.
To sum up, this application fills in the three-dimensional porous support of copper foil surface electrostatic spinning three-dimensional nano wire through the metallic lithium embedding, realizes effectively reducing local current density, and the deposit of homogenization lithium ion, and then the growth of restraining lithium dendrite reduces the lithium ion deposit overpotential to adapt to the volume change of battery circulation in-process, avoid dying lithium and generate, and then improve coulomb efficiency, greatly increased lithium metal battery's security.
The above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions in the embodiments of the present application.
Claims (10)
1. A three-dimensional lithium metal electrode comprising a three-dimensional porous scaffold and metallic lithium intercalated into the three-dimensional porous scaffold;
the three-dimensional porous scaffold comprises a precursor material and a metal foil.
2. The three-dimensional lithium metal electrode of claim 1, wherein the precursor material is a perovskite material and the metal foil is a copper foil.
3. The three-dimensional lithium metal electrode according to claim 1, wherein the precursor material is selected from (La)0.6Sr0.4)0.95Co0.2Fe0.8O3-Or Ba0.5Sr0.5Co0.2Fe0.8O3-Wherein 0 < 3.
4. The three-dimensional lithium metal electrode according to claim 3, wherein the precursor material is prepared by:
metal salt is added according to the molar ratio of (La: Sr): (Co: Fe) (0.6:0.4)0.95:(0.2:0.8)1Or (Ba: Sr): (Co: Fe) ═ 0.5:0.5:0.2:0.8 is added into the solvent, then the polymer matrix is added, and the mixture is mixed, so as to obtain the precursor material.
5. The three-dimensional lithium metal electrode as claimed in claim 4, wherein the ratio of the metal salt to the solvent is 1mmol (2-5) ml, and the mass ratio of the metal salt to the polymer matrix is 1 (4-8)%.
6. The three-dimensional lithium metal electrode according to claim 4, wherein the metal salt is selected from La (NO)3)2·6H2O、Ba(NO3)2、Sr(NO3)2、Co(NO3)2·6H2O and Fe (NO)3)3·9H2And O.
7. The three-dimensional lithium metal electrode according to claim 4, wherein the solvent is selected from the group consisting of N, N-dimethylformamide, ethanol, and water;
the polymer matrix is selected from polyacrylonitrile, polyvinylpyrrolidone, polyvinyl butyral or polyvinyl alcohol.
8. A method for preparing a three-dimensional lithium metal electrode according to any one of claims 1 to 7, comprising the steps of:
step a: carrying out electrostatic spinning on the precursor material to the metal foil, drying and sintering to obtain the three-dimensional porous support;
step b: and filling the lithium metal melted at high temperature into the three-dimensional porous support to obtain the three-dimensional lithium metal electrode.
9. The preparation method according to claim 8, wherein the applied voltage of the electrostatic spinning is 10-20kV, the drying temperature is 50-100 ℃, the sintering temperature is (800-1000) DEG C, and the sintering time is 3-5 h;
the temperature of the high-temperature melting is 200-400 ℃.
10. A lithium metal battery comprising the three-dimensional lithium metal electrode according to any one of claims 1 to 7.
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| CN114270575A (en) * | 2021-03-31 | 2022-04-01 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
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