CN111668493A - Three-dimensional current collector for inhibiting dendritic crystal of lithium metal negative electrode and application of three-dimensional current collector in metal lithium battery - Google Patents
Three-dimensional current collector for inhibiting dendritic crystal of lithium metal negative electrode and application of three-dimensional current collector in metal lithium battery Download PDFInfo
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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
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A three-dimensional current collector for inhibiting dendritic crystals of a lithium metal negative electrode and application of the three-dimensional current collector in a metal lithium battery belong to the technical field of batteries. The three-dimensional current collector is a copper foil loaded Cu @ Sn nanocone array structure current collector. The current collector frame with the three-dimensional nanocone array structure can effectively relieve the volume expansion of lithium metal in the circulation process, the high specific surface area of the current collector frame can reduce the average current density, disperse an electric field and promote the uniform deposition of lithium; the Li-Sn alloy is formed in situ by the Li-philic Sn nano particles and lithium in the circulation process to form uniform lithium nucleation sites, so that the polarization of lithium deposition is reduced, and the uniform deposition/dissolution of lithium is induced. From the point of nucleation and deposition, the synergistic effect of the two can effectively inhibit the growth of lithium dendrites, and improve the coulombic efficiency and the cycle stability of the battery. The current collector has the characteristics of light weight, small volume and lithium affinity, has small influence on the energy density of the battery, and liquid and solid metal lithium batteries based on the current collector show good cycle stability.
Description
Technical Field
The invention belongs to the technical field of chemical power supplies, particularly lithium metal batteries, and particularly relates to a three-dimensional current collector for inhibiting dendritic crystals of a lithium metal negative electrode and application of the three-dimensional current collector in a lithium metal battery.
Background
The method has the advantages of developing clean energy, constructing a safe, efficient, clean and sustainable energy new system, reducing the use of fossil energy by traditional industries and automobiles, and having important influence on the sustainable development of human society. In recent years, new energy automobiles are rapidly developed as a new industry and an important field of national strategy under the continuous guidance promotion of policies. The battery system is used as the power core of the electric automobile, and the energy density and the safety performance of the battery system can directly influence the endurance mileage and the safety of the electric automobile, so that research and development of the battery system with high energy density and safety and reliability are the core of the development of new energy electric automobiles. Compared with the traditional graphite cathode, the lithium metal has high theoretical specific capacity (3860mAh g)-1) And the most negative reduction potential (-3.04vvs. standard hydrogen electrode), are considered to be the most ideal negative electrode material, and batteries based on metallic lithium as the negative electrode (such as Li-S, Li-air, etc.) are also considered to be the next generation ideal battery system.
However, the application of the lithium metal negative electrode has the following problems: on one hand, in the process of deposition/dissolution of lithium metal, due to different liquid phase mass transfer flows of local lithium ions, uneven deposition on a current collector can be caused, lithium dendrite is generated, the continuous growth of the lithium dendrite can pierce through a diaphragm, the battery is short-circuited, the safety problem is caused, and in the process of lithium stripping, the lithium metal can fall off from the root first, so that part of lithium loses electric contact and becomes dead lithium, and the coulomb efficiency of the battery is reduced; in addition, serious problems such as volume expansion and the like are caused in the repeated charge and discharge process, so that the SEI film is continuously reconstructed, and the coulombic efficiency and the cycle life are reduced.
Existing improvement methods include electrolyte additives, artificial SEI films, solid electrolytes, three-dimensional current collectors, and the like. Compared with a planar current collector, the three-dimensional current collector has a large surface area, so that lithium dendrites can be inhibited to a certain degree, and the three-dimensional structure of the three-dimensional current collector can be used as a lithium storage frame to relieve the problems of volume expansion and the like of a negative electrode. However, the current commercialized three-dimensional copper foam current collector has large mass and thick volume, reduces the energy density of the battery, shows lithium-phobicity, is not beneficial to uniform deposition of lithium, and needs to develop a three-dimensional copper current collector with light mass, small volume and lithium-philic property.
Disclosure of Invention
The invention aims to solve the problems of large mass, thick volume, lithium phobicity and the like of the existing commercialized three-dimensional foam copper current collector, and provides a three-dimensional current collector for inhibiting dendritic crystals of a lithium metal negative electrode and application thereof in a metal lithium battery. The novel three-dimensional current collector provided by the invention adopts a Cu @ Sn nanocone array structure, can promote uniform nucleation and deposition of lithium, effectively inhibits lithium dendrites, and improves the safety performance of a metal lithium battery. The current collector has the characteristics of light weight, small volume and lithium affinity, has small influence on the energy density of the battery, and liquid and solid metal lithium batteries based on the current collector show good cycle stability.
Technical scheme of the invention
A three-dimensional current collector for inhibiting dendritic crystals of a lithium metal negative electrode is a Cu @ Sn three-dimensional nanocone array structure current collector loaded by a copper foil. The three-dimensional current collector comprises a copper foil substrate and a three-dimensional nanocone array decorated by tin nanoparticles on the surface of the substrate. The invention directly modifies a plane copper foil substrate (commercial plane copper foil) to prepare the current collector with the three-dimensional Cu @ Sn nanocone array structure.
The preparation method of the three-dimensional current collector for inhibiting the dendritic crystal of the lithium metal negative electrode provided by the invention comprises the following stepsTreating the copper foil substrate for 10-30min under a constant potential of-1.12V by using a three-electrode system in an electrolytic cell; then using a three-electrode system in an electrolytic cell to make the system be 3.3mAcm-2The three-dimensional nanocone array on the surface of the copper foil substrate is processed for 20-60s under the constant current density.
In the first step the electrolytic cell solution composition comprises CuSO4·5H2O、NiSO4·6H2O、NaH2PO2、Na3C6H5O7、H3BO3PEG, NaOH and CuSO4·5H2O、NiSO4·6H2O、NaH2PO2、Na3C6H5O7、H3BO3The quantity ratio of the PEG substance is 100-300:10-30:1000-3000:200-500:1000-5000:1-3, and the pH range of the solution is 7.0-9.0; the working electrode in the three-electrode system is a copper foil substrate, the counter electrode is a Pt sheet, and the reference electrode is a saturated Ag/AgCl electrode.
In the second step, the composition of the electrolytic cell solution is Na3C6H5O7、SnSO4And NaOH, Na3C6H5O7、SnSO4The mass ratio of the substances is 10-50:1-3, and the pH range of the solution is 7.0-9.0; the working electrode in the three-electrode system is a three-dimensional nano-cone array, the counter electrode is a Pt sheet, and the reference electrode is a saturated Ag/AgCl electrode.
Pretreatment is required before the copper foil substrate is treated; the pretreatment is to clean the copper foil with sulfuric acid, acetone, absolute ethyl alcohol and ultrapure water in sequence.
The invention also provides the application of the three-dimensional current collector for inhibiting the dendritic crystal of the lithium metal negative electrode in the metal lithium battery, the three-dimensional current collector is used for a composite lithium metal negative electrode in the metal lithium battery, and the embedding method of the metal lithium is an electrochemical deposition method or a molten pouring method.
The invention has the advantages and beneficial effects that:
the invention provides a three-dimensional current collector for inhibiting dendritic crystals of a lithium metal negative electrode and application of the three-dimensional current collector in a metal lithium battery, wherein the three-dimensional current collector is a copper nano cone array structure directly obtained on commercial planar copper foil through an electrochemical deposition method, and then tin nanoparticles are modified on the surface of a nano cone through an electrodeposition method to obtain the three-dimensional Cu @ Sn nano cone array structure current collector. Wherein, tin and lithium can form an alloy which is used as an initial lithium nucleation site to induce lithium to be uniformly nucleated and reduce polarization of lithium deposition; the nano-cone array structure can disperse an electric field, reduce the average current density, make lithium ions distributed more uniformly and promote the uniform deposition of lithium. From the point of nucleation and deposition, the synergistic effect of the two can effectively inhibit the growth of lithium dendrites. The current collector is used for liquid and solid metal lithium batteries, and shows good cycle stability. The current collector has the characteristics of light weight, small volume and lithium affinity, and has small influence on the energy density of the battery.
Drawings
FIG. 1 is a scanning electron micrograph of a three-dimensional copper nanocone according to example 1;
FIG. 2 is a scanning electron micrograph of a three-dimensional Cu @ Sn nanocone prepared with a tin deposition time of 20s in example 2;
FIG. 3 is the deposition profile of lithium on Cu @ Sn nanocones in example 3;
FIG. 4 is a graph of the voltage of lithium deposition on copper foil, copper nanocone, Cu @ Sn nanocone, respectively, in example 4;
FIG. 5 shows the cell density at 1mAcm for the symmetrical cell obtained in example 5-2Carrying out charge and discharge for each 1h of cycle test curve under current density;
fig. 6 is a graph of liquid cell cycle performance based on Cu @ Sn nanocone current collectors in example 6;
fig. 7 is a graph of solid state battery cycle performance based on Cu @ Sn nanocone current collectors in example 7.
Detailed Description
The present invention will be further described below with reference to the accompanying drawings for easier understanding, but the present invention can be implemented in various forms, and is not limited to the embodiments described herein and does not constitute any limitation to the present invention.
Example 1:
this example describes the topography of a copper nanocone array.
Commercial copper foil 0.5M H, respectively2SO4Soaking in acetone and absolute ethyl alcohol for half an hour, and washing with ultrapure water.
Preparing electrolyte: 100mL of ultrapure water was added to a beaker, and 0.75g of CuSO was added thereto4·5H2O、0.063gNiSO4·6H2O，2.112g NaH2PO2，1.47g Na3C6H5O7，3.09g H3BO3And 0.6g PEG to give a blue, transparent mixed solution, which was adjusted to pH 8.0 with NaOH.
The pretreated copper foil is used as a working electrode, a Pt sheet counter electrode and a saturated Ag/AgCl electrode as a reference electrode, an electrochemical workstation is used for carrying out constant-voltage electrodeposition, and the set conditions are as follows: heating and stirring at-1.12V and 75 deg.C, depositing for 1800s, and rotating at 150rmin-1Soaking the deposited copper foil in 0.1M H deg.C2SO4And (5) washing with ultrapure water for 1h, and drying by using a vacuum oven to obtain the copper nanocone array.
FIG. 1 is a scanning electron micrograph of the surface of the copper nanocone obtained in example 1. A layer of compact nano cone array is uniformly covered on the surface of the copper foil, and the length of the cone is about 5 mu m. A
Example 2
This example describes the morphology of a Cu @ Sn nanocone.
Copper nanocone array preparation same as example 1 except that 0.55g of CuSO was added to 100mL of ultrapure water4·5H2O、0.046g NiSO4·6H2O，1.86g NaH2PO2，1.04g Na3C6H5O7，2.78g H3BO3And 0.3g PEG, pH adjusted to 8.5 with NaOH.
Preparing electrolyte: 100mL of ultrapure water was added to a beaker, and 8.0g of NaOH and 2.941g of Na were added, respectively3C6H5O7And 1.0735g SnSO4Uniformly stirring the mixture to prepare a mixed solution,
using Cu nanocone as working electrode, Pt sheet as counter electrode, and saturated Ag/AgCl electrode as reference electrodeElectrochemical workstation at 3.3mAcm-2Constant current electrodeposition is carried out under the conditions of current density and stirring, the deposition time is 20s, and the rotating speed is 150rmin-1And after the deposition is finished, washing with ultrapure water, and drying in a vacuum drying oven to obtain the Cu @ Sn nanocone.
Fig. 2 is an SEM image of a Cu @ Sn nanocone array current collector; tin is uniformly distributed on the surface of the nanocone, which is helpful for forming uniform nucleation sites.
Example 3
The embodiment researches the deposition morphology of lithium on a Cu @ Sn nanocone
Lithium foil as negative electrode, 1M LiTFSI DOL/DME (volume ratio 1:1) + 1% LiNO3Half-cells were assembled in an argon glove box at 1mA cm for electrolyte, Celgard2400 for separator, Cu @ Sn nanopyramids prepared on the basis of example 1 for positive electrode-2After discharging for 2h under the current density, the battery is disassembled in an argon glove box, the surface of the Cu @ Sn nanocone electrode is washed by dimethyl ether (DME), and SEM test is carried out after drying.
FIG. 3 is the deposition capacity of lithium on Cu @ Sn nanocones of example 3 of 2mAh cm-2The morphology of the sample. The three-dimensional nanocone structure enables the electric field distribution to be more uniform, the charge distribution to be relatively uniform, the lithium deposition to be more uniform, the dendritic morphology cannot be observed on the surface, and a relatively flat plane is formed; meanwhile, the uniform distribution of Sn on the nanocones can form uniform initial lithium nucleation sites, and the deposition of lithium is regulated and controlled, so that the deposition of lithium is more uniform. Under the synergistic effect of the two, a relatively uniform and flat lithium deposition plane is formed.
Example 4
This example tests the voltage profiles of lithium deposition on copper foil, copper nanocone, and a Cu @ Sn nanocone prepared with a tin deposition time of 20s, respectively.
Lithium foil as negative electrode, 1M LiTFSI DOL/DME (volume ratio 1:1) + 1% LiNO3Assembling a half cell in an argon glove box by using electrolyte, Celgard2400 as a diaphragm and copper foil or Cu @ Sn nanocone as an anode at 1mAcm-2Discharging at current density to obtain a discharge curve.
FIG. 4 shows the half-cell of example 4 at 1mAcm-2At current densityThe deposition voltage profile of (1). Due to the fact that the three-dimensional structure of the Cu nanocone has a large surface area, local current density can be reduced, and the overpotential of lithium deposited on the Cu nanocone is smaller than that of the Cu foil. Compared with Cu foil and Cu nanocones, Li ions firstly react with Sn to form Li-Sn alloy due to modification of Sn, a large number of active sites are provided to promote Li nucleation, and therefore the Cu @ Sn nanocone current collector shows lower nucleation overpotential.
Example 5
This example tested 1mAcm-2The lithium symmetrical battery is based on a copper foil and a Cu @ Sn nanocone current collector under the current density.
The electrode is prepared by pre-depositing lithium on a copper foil or a Cu @ Sn nanocone: lithium foil as negative electrode, 1M LiTFSI DOL/DME (volume ratio 1:1) + 1% LiNO3Assembling a half cell in an argon glove box by using electrolyte, Celgard2400 as a diaphragm and copper foil or Cu @ Sn nanocone as an anode at 1mAcm-2Discharging for 3h under current density, disassembling the battery to obtain the pre-deposition capacity of 3mAh cm-2The negative electrode of (1).
The above-mentioned electrodes were used as positive and negative electrodes, 1M LiTFSI DOL/DME (volume ratio 1:1) + 1% LiNO3The electrolyte and Celgard2400 separator were used to assemble a symmetrical cell at 1mAcm in an argon glove box-2And carrying out 1h cycle test of charging and discharging under current density.
FIG. 5 shows the cell density at 1mAcm for the symmetrical cell obtained in example 5-2And carrying out charge and discharge under current density for each 1h cycle test curve. The symmetrical cell based on the Cu @ Sn nanocone shows smaller overpotential and better cycle stability.
Example 6
The cycle performance of the liquid metal lithium battery based on the three-dimensional Cu @ Sn nanocone current collector is tested in the embodiment.
The anode active material adopts LiFePO4。LiFePO4Uniformly mixing SuperP and Polytetrafluoroethylene (PTFE) emulsion according to the mass ratio of 8:1:1, grinding for 30min, dispersing in N-methyl pyrrolidone (NMP), homogenizing in a homogenizer for 20min to obtain uniform slurry, coating the slurry on an aluminum foil by a scraper, drying in a vacuum drying oven at 80 ℃ for 12h, and cutting into pieces by a smashing machineAnd a positive electrode plate.
The negative electrode is prepared by pre-depositing lithium on a Cu @ Sn nanocone: lithium foil as negative electrode, 1M LiTFSI DOL/DME (volume ratio 1:1) + 1% LiNO3Assembling a half cell in an argon glove box by taking electrolyte, Celgard2400 as a diaphragm and Cu @ Sn nanocones as an anode at 1mAcm-2Discharging for 3h under current density to obtain a pre-deposition capacity of 3mAh cm-2The negative electrode of (1).
The Cu @ Sn nano-cone cathode and the anode electrode plate of the pre-deposited lithium, 1M LiTFSI DOL/DME (volume ratio is 1:1) + 1% LiNO3And (3) assembling the electrolyte and the Celgard2400 diaphragm into a liquid metal lithium battery in an argon glove box.
FIG. 6 is a graph showing the cycle performance at 1C rate of the liquid metal lithium battery obtained in example 6, wherein the discharge capacity of the liquid metal lithium battery does not decrease after 300 cycles at 1C rate;
example 7
The cycle performance of the solid-state metal lithium battery based on the three-dimensional Cu @ Sn nanocone current collector is tested in the embodiment.
The preparation of the positive electrode and the negative electrode are the same as those in example 6.
Preparing a solid electrolyte: 2.0g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) and nano SiO2The particles were dispersed in 15mL of acetone, stirred at 50 ℃ for 2h, scraped on aluminum foil with a prep, and vacuum dried at 100 ℃ for 12 h. After cooling to room temperature, the membrane was soaked in 1M LiTFSI DOL/DME (1: 1 by volume) + 1% LiNO3After 24 hours in the electrolyte, the residual electrolyte on the membrane surface was wiped off with filter paper before use.
And assembling the positive electrode plate, the negative electrode plate and the solid electrolyte into the solid metal lithium battery in an argon glove box.
Fig. 7 is a graph of the cycle performance of the solid-state battery obtained in example 7 at room temperature under the rate of 1C, and the discharge capacity of the solid-state battery obtained under the rate of 1C is not attenuated after 300 cycles, which indicates that the solid-state battery based on the Cu @ Sn nanocone current collector has good cycle stability.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. The three-dimensional current collector is characterized by being a copper foil loaded current collector with a Cu @ Sn three-dimensional nanocone array structure.
2. The three-dimensional current collector for suppressing lithium metal negative dendrites of claim 1 wherein the three-dimensional current collector comprises a copper foil substrate, a three-dimensional nanocone array with tin nanoparticle decorated substrate surface, the copper foil substrate being a commercial planar copper foil.
3. The three-dimensional current collector for suppressing the dendrite of the lithium metal negative electrode according to claim 2, wherein the three-dimensional nanocone array is prepared by treating a copper foil substrate with a three-electrode system at a constant potential of-1.12V for 10-30min in an electrolytic cell.
4. The three-dimensional current collector for suppressing lithium metal negative dendrites of claim 3 wherein a three-dimensional nanocone array of copper foil substrate surface is prepared, the electrolytic cell solution composition comprises CuSO4·5H2O、NiSO4·6H2O、NaH2PO2、Na3C6H5O7、H3BO3PEG, NaOH and CuSO4·5H2O、NiSO4·6H2O、NaH2PO2、Na3C6H5O7、H3BO3The quantity ratio of the PEG substance is 100-300:10-30:1000-3000:200-500:1000-5000:1-3, and the pH range of the solution is 7.0-9.0; the working electrode in the three-electrode system is a copper foil substrate, the counter electrode is a Pt sheet, and the reference electrode is a saturated Ag/AgCl electrode.
5. According to claimThe three-dimensional current collector for inhibiting the dendritic crystal of the lithium metal negative electrode is characterized in that the modification method of the tin nano-particles is to use a three-electrode system in an electrolytic cell at 3.3mAcm-2The three-dimensional nanocone array on the surface of the copper foil substrate is processed under the constant current density, and the processing time is 20-60 s.
6. The three-dimensional current collector for suppressing lithium metal negative dendrites of claim 5 wherein the cell solution composition is Na3C6H5O7、SnSO4And NaOH, Na3C6H5O7、SnSO4The mass ratio of the substances is 10-50:1-3, and the pH range of the solution is 7.0-9.0; the working electrode in the three-electrode system is a three-dimensional nano-cone array, the counter electrode is a Pt sheet, and the reference electrode is a saturated Ag/AgCl electrode.
7. The application of a three-dimensional current collector for inhibiting dendritic crystals of a lithium metal negative electrode in a metal lithium battery is used for a composite lithium metal negative electrode in the metal lithium battery, and the embedding method of the metal lithium is an electrochemical deposition method or a fusion perfusion method.
8. The use according to claim 7, wherein the lithium metal battery comprises liquid and solid state lithium metal batteries, and the lithium metal negative electrode current collector is the three-dimensional current collector according to any one of claims 1 to 6.
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