CN112490411B - Method for protecting lithium metal negative electrode through in-situ film forming - Google Patents
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Abstract
A method for protecting a lithium metal negative electrode by in-situ film forming aims to solve the problems that an existing method for inhibiting the growth of lithium dendrites of a lithium metal battery is difficult to form a uniform protective film and the protection effect is poor. The method for protecting the lithium metal negative electrode by in-situ film forming comprises the following steps: firstly, preparing an alumina precursor sol, coating the alumina precursor sol on a conductive substrate in a spinning mode, and preserving heat in a muffle furnace at the temperature of 630-680 ℃ to obtain the conductive substrate loaded with a transition solid electrolyte membrane; and secondly, placing the polished metal material on a conductive substrate loaded with a transition solid electrolyte membrane under the protection of argon, clamping and then applying negative voltage and positive voltage to the conductive substrate and the metal material respectively to carry out anodic oxidation treatment. The cycle life of the lithium metal full cell protected by the anodic oxidation in-situ membrane is prolonged from 76 turns to 300 turns of the unprotected lithium metal full cell. The stability of the lithium metal electrode modified by the in-situ protection material is obviously improved.
Description
Technical Field
The invention relates to the field of lithium metal electrode protection materials, in particular to a method for protecting a lithium metal negative electrode through in-situ film forming.
Background
The development of energy storage materials is an inherent driving force for the advancement of modern technology. In the fields of electric vehicles, energy storage and current hot robots, energy storage technology plays a very important role. The energy density, volume and morphology of the battery directly determine the range of applications of the power supply system. For example, lithium ion batteries with high energy density are becoming increasingly thinner for mobile phones and notebooks. However, the theoretical capacity of the graphite anode used by the traditional lithium ion battery is smaller and is only 372mAh/g, which limits the further improvement of the battery capacity. Lithium metal anodes have a high theoretical capacity of 3860mAh/g, which makes them well suited for use in lithium ion batteries and has been considered as ideal anodes in lithium battery systems over the last 40 years. However, the formation of dendrites on lithium metal presents safety problems due to the possibility of short circuits and explosions. Major obstacles have hindered the widespread practical use of long-term lithium metal batteries. Therefore, it is necessary to develop a highly effective protection technique for suppressing dendrites. To date, a number of surface modification methods have been developed. Among them, the artificial protective film has attracted people's attention due to its special protective effect and high practical value. It is reported that the in-situ protective film is an efficient protective film. The in situ growth strategy produces a uniform film that adheres tightly to the substrate surface without any adhesive. However, the design synthesis and protective effects of in situ membranes still need to be further improved. Anodized films have been used to protect metal surfaces, such as aluminum or titanium. When aluminum is made into the anode of an electrolytic cell, the type of anodic oxide film that can be produced on the aluminum depends on several factors, the most important of which is the nature of the electrolyte. The electrolyte in which the formed oxide film is completely insoluble is an important factor for producing a barrier type film. With lithium metal, since it is partially soluble in the electrolyte and the peeling is not uniform, it is difficult to form a uniform anodic oxide film. To date, no technique for producing an anodic oxide film on lithium metal has been reported. Therefore, if a solid electrolyte (an organic or inorganic compound that can transport ions) in which the oxide film formed at the anode is completely insoluble is used, a stable anodic oxide film can be grown on the lithium metal surface.
Disclosure of Invention
The invention aims to solve the problems that the existing method for inhibiting the growth of lithium dendrite is difficult to form a uniform protective film and the protection effect is poor, thereby providing a method for in-situ film formation to protect a lithium metal negative electrode.
The method for protecting the lithium metal negative electrode by in-situ film forming is realized according to the following steps:
firstly, preparing a transition electrolyte membrane:
a. adding isopropanol aluminum powder into an ethylene glycol ethyl ether solvent, performing ultrasonic dispersion uniformly to obtain a mixed solution, stirring for 20-40 minutes at 60-80 ℃, then adding an acetylacetone complexing agent, continuing to perform stirring reaction at 60-80 ℃, finally adding glacial acetic acid, performing stirring reaction for 20-40 minutes at 100-120 ℃, cooling to room temperature, and filtering to obtain a (transparent and clear) alumina precursor sol;
b. spin coating the alumina precursor sol on a conductive substrate, heating and curing, and repeating spin coating and heating and curing for multiple times to obtain an alumina film;
c. placing the alumina film in a muffle furnace, heating to 630-680 ℃ at the speed of 1 ℃/min, preserving heat, and naturally cooling to room temperature to obtain a conductive substrate loaded with a transition solid electrolyte film;
secondly, preparing the metal electrode protected by the in-situ film:
polishing the metal material, placing the polished metal material on a conductive substrate loaded with a transition solid electrolyte membrane under the protection of argon, clamping, and then respectively applying negative voltage and positive voltage to the conductive substrate and the metal material to carry out anodic oxidation treatment, namely obtaining an in-situ protective membrane on the surface of the metal material.
The invention firstly synthesizes ultrathin modified amorphous Al by a sol-gel method2O3Solid electrolyte, and can be in the lithium metal/Al2O3A stable anodic oxidation protection film is formed in situ at the interface of the solid electrolyte. The anodic oxidation of lithium metal was experimentally achieved for the first time and an excellent in-situ protective film was obtained.
The method for protecting the lithium metal negative electrode by in-situ film forming comprises the following beneficial effects:
1. the lithium metal under the protection of the in-situ membrane material not only reduces the solid-solid interface impedance between the bare lithium and the common ex-situ protection membrane, but also is beneficial to improving the stability of the lithium metal electrode.
2. The full cell composed of lithium metal and lithium cobaltate anode under the protection of the in-situ membrane material of the invention has the effective cycle number of 300 times when commercial 1M LiPF6 EC DMC is used and no additive which is beneficial to the stability of SEI membrane is added, while the full cell composed of bare copper electrode can only stably cycle 76 times.
3. The in-situ membrane material of the solid anodic oxidation technology of the metal electrode does not contain precious metal components, has low cost and simple and convenient preparation process; the source is wide, and the film is rich in carbon element, so that the film is environment-friendly.
Drawings
FIG. 1 is a time-current curve of a solid-state anodization process of dilithium metal of an example;
FIG. 2 is an SEM photograph of an in-situ protective film on a lithium metal surface prepared in example II;
FIG. 3 is a graph showing cycle comparison of a bare lithium/lithium cobaltate full cell and a full cell of lithium metal and lithium cobaltate protected by an in-situ protective film prepared in example one and example two; wherein 1 is a cycle capacity curve of a bare lithium/lithium cobaltate full battery; 2 is the cycle capacity curve of the protected lithium/lithium cobaltate full cell prepared in example one and example two; 3 is the protected lithium/lithium cobaltate full cell coulombic efficiency change curve prepared in the first and second examples; 4, a change curve of the coulombic efficiency of the bare lithium/lithium cobaltate full battery;
FIG. 4 is a comparison graph of XPS test results of an in-situ protective film protected lithium metal surface and a bare lithium surface prepared in example one and example two; wherein 1, the C1s spectrogram of the protected lithium surface prepared in the first embodiment and the second embodiment, and 2 is the C1s spectrogram of a naked lithium surface;
FIG. 5 is a comparison of XPS test results for a fluorine-containing in-situ protective film protected lithium metal surface and a bare lithium surface formed by anodic oxidation of HFE prepared in example three; wherein 1 the spectrum of F1s for the protected lithium surface prepared in example three, and 2 is the spectrum of F1s for the bare lithium surface;
fig. 6 is a graph of the cycle charge and discharge test of the full cell composed of lithium metal and lithium cobaltate protected by the fluorine-containing in-situ protective film formed by HFE anodic oxidation prepared in example three, wherein 1 is coulombic efficiency, and 2 is specific capacity.
Detailed Description
The first embodiment is as follows: the method for protecting the lithium metal negative electrode by in-situ film formation is implemented according to the following steps:
firstly, preparing a transition electrolyte membrane:
a. adding isopropanol aluminum powder into an ethylene glycol ethyl ether solvent, performing ultrasonic dispersion uniformly to obtain a mixed solution, stirring for 20-40 minutes at 60-80 ℃, then adding an acetylacetone complexing agent, continuing to perform stirring reaction at 60-80 ℃, finally adding glacial acetic acid, performing stirring reaction for 20-40 minutes at 100-120 ℃, cooling to room temperature, and filtering to obtain a (transparent and clear) alumina precursor sol;
b. spin coating the alumina precursor sol on a conductive substrate, heating and curing, and repeating spin coating and heating and curing for multiple times to obtain an alumina film;
c. placing the alumina film in a muffle furnace, heating to 630-680 ℃ at the speed of 1 ℃/min, preserving heat for 2h, and naturally cooling to room temperature to obtain a conductive substrate loaded with a transition solid electrolyte film;
secondly, preparing the metal electrode protected by the in-situ film:
polishing the metal material, placing the polished metal material on a conductive substrate loaded with a transition solid electrolyte membrane under the protection of argon, clamping, and then respectively applying negative voltage and positive voltage to the conductive substrate and the metal material to carry out anodic oxidation treatment, namely obtaining an in-situ protective membrane on the surface of the metal material.
The embodiment develops an in-situ protection layer preparation technology with low cost and simple preparation process, and obtains the stable lithium metal in-situ protection film by utilizing the incompatibility of the transition solid electrolyte and the metal material anodic oxide film. The in-situ protective film formed based on the solid-state anodic oxidation technology has the functions of homogenizing ion flow and eliminating/inhibiting the growth of lithium dendrites, is simple to manufacture and environment-friendly, and solves the problem that the existing method for inhibiting the growth of the lithium dendrites needs to be heated at high temperature in a glove box to melt lithium metal with active chemical properties, so that certain potential safety hazards exist.
The second embodiment is as follows: the difference between the present embodiment and the first embodiment is that the alumina precursor sol in step a is further added with a nano powder material, wherein the nano powder material is MoO3Nano powder, ZnO nano powder, TiO2Nano powder, NiO nano powder, Ni2O3Nano powder and Al2O3Nano powder and Bi2O3Nano powder, ZnFe2O4Nano powder or CuBi2O4And (3) nano powder.
The incorporation of nanopowder materials in the present embodiment, in the form of spheres, plates, rods, horns or sponges, contributes to the intra-membrane ion transport.
The third concrete implementation mode: the second difference between the present embodiment and the specific embodiment is that the preparation method of the ZnO nanopowder is as follows: weighing 2 parts of zinc nitrate and 1 part of sodium hydroxide according to the parts by weight, mixing and grinding the zinc nitrate and the sodium hydroxide for 20-50 min to obtain precursor slurry; and annealing the precursor slurry at the temperature of 250 ℃ to obtain ZnO nanorod powder.
The fourth concrete implementation mode: the second difference between the present embodiment and the specific embodiment is that the nano powder material is added into the mixed solution, and the concentration of the nano powder material in the mixed solution is 10 to 50 mmol/L.
The fifth concrete implementation mode: the difference between the first embodiment and the fourth embodiment is that in the step b, a spin coater is used to spin-coat the alumina precursor sol on the conductive substrate, and the rotation speed of the spin coater is controlled to be 1000-3000 rpm.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is that step c is to drop a protective film composition control solution onto the conductive substrate loaded with the transition solid electrolyte film, where the protective film composition control solution is one or more of a fluorinated solvent (such as HFE), a lithium difluorophosphate solution, a lithium nitrate solution, and a LiFSI solution.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is that the thickness of the transition solid electrolyte film on the conductive substrate in step c is 0.1 to 30 μm.
The specific implementation mode is eight: the difference between this embodiment mode and one of the first to seventh embodiment modes is that the conductive substrate in the second step is a silicon wafer, a platinum sheet, an aluminum sheet or a gold-plated sheet.
The specific implementation method nine: the present embodiment is different from the first to eighth embodiments in that the metal material in the second step is a lithium metal negative electrode, a zinc metal negative electrode, a sodium metal negative electrode, a magnesium metal negative electrode, or an aluminum metal negative electrode.
The detailed implementation mode is ten: the difference between this embodiment and the first to ninth embodiments is that in the second step, the anodic oxidation voltage is controlled to be 1-30V and the anodic oxidation time is controlled to be 10-1000 s.
The concrete implementation mode eleven: the difference between this embodiment and the first to tenth embodiments is that the thickness of the in-situ protection film in the second step is 1 to 20 μm.
The first embodiment is as follows: the method for protecting the lithium metal negative electrode by in-situ film formation is implemented according to the following steps:
firstly, preparing a transition electrolyte membrane:
a. adding 0.02mol of isopropanol aluminum powder into 50mL of ethylene glycol ethyl ether solvent, performing ultrasonic dispersion for 20 minutes to obtain a mixed solution, stirring for 30 minutes at 70 ℃, keeping the heating state, then adding 0.02mol of acetylacetone complexing agent, continuing stirring for reaction for 30 minutes at 70 ℃, finally adding 10mL of glacial acetic acid, stirring for reaction for 30 minutes at 110 ℃, cooling to room temperature, and filtering to obtain transparent and clear alumina precursor sol;
b. fixing a 2 x 2cm conductive substrate on a spin coater, spin-coating an alumina precursor sol on the conductive substrate, starting the spin coater to spin, wherein the spin time is 20s, performing heat treatment in a three-section furnace at 150 ℃, 300 ℃ and 450 ℃ for 2 min, and repeating the processes of spin-coating the sol and heating and curing for 6 times to obtain an alumina film with the thickness of 210 nm;
c. placing the alumina membrane in a muffle furnace, heating to 650 ℃ at the speed of 1 ℃/min, preserving the heat for 2h, and naturally cooling to room temperature to obtain a conductive substrate loaded with a transition solid electrolyte membrane;
example two: preparing an in-situ membrane protected metal electrode:
polishing a lithium metal material, placing the polished metal material on a conductive substrate loaded with a transition solid electrolyte membrane in an argon-protected glove box, clamping two surfaces of the conductive substrate and the metal material by using a clamp, respectively applying negative voltage and positive voltage to the conductive substrate and the metal material, and carrying out anodic oxidation treatment, wherein the anodic oxidation voltage is controlled to be 10V; the time of anodic oxidation treatment is 400s, namely an in-situ protective film is obtained on the surface of the metal material.
Example three: preparing a metal electrode protected by a fluorine-containing in-situ membrane:
in a glove box protected by argon, a fluorine-containing solvent is dripped on a transition solid electrolyte membrane, a metal material is polished, then the polished metal material is placed on a conductive substrate loaded with the transition solid electrolyte membrane, two sides of the conductive substrate and the metal material are clamped by clamps and respectively applied with negative voltage and positive voltage, anodic oxidation treatment is carried out, and the anodic oxidation voltage is controlled to be 10V; the time of anodic oxidation treatment is 400s, namely an in-situ protective film is obtained on the surface of the metal material.
The fluorine-containing solvent described in this example is Hydrofluoroether (HFE), LiFSI solvent, or fluoroethylene carbonate (FEC).
Example four: preparing a metal electrode protected by a nitrogen-containing in-situ film:
in a glove box protected by argon, dripping a lithium nitrate solvent on a transition solid electrolyte membrane, polishing a metal material, then placing the polished metal material on a conductive substrate loaded with the transition solid electrolyte membrane, clamping the two surfaces by using a clamp, applying negative voltage and positive voltage to the conductive substrate and the metal material respectively, carrying out anodic oxidation treatment, and controlling the anodic oxidation voltage to be 10V; the time of anodic oxidation treatment is 400s, namely an in-situ protective film is obtained on the surface of the metal material.
Example five: preparing a metal electrode protected by an in-situ film containing a fluorine and nitrogen double-element compound:
in an argon-protected glove box, dropping an FEC solution with the concentration of 0.5mol/L lithium nitrate on a transition solid electrolyte membrane, polishing a metal material, then placing the polished metal material on a conductive substrate loaded with the transition solid electrolyte membrane, clamping two surfaces by using a clamp, applying negative voltage and positive voltage to the conductive substrate and the metal material respectively, carrying out anodic oxidation treatment, and controlling the anodic oxidation voltage to be 10V; and (4) anodizing for 400-1000 s to obtain the in-situ protective film on the surface of the metal material.
Solid state anodization process testing:
the solid-state anodization time-current curve was tested using the Shanghai Chenghua CHI760E electrochemical workstation. The setting time is 400s, the voltage is 10V, the negative electrode clamps a conductive substrate, the positive electrode clamps lithium metal, and the conductive substrate and the positive electrode are clamped in a glove box protected by argon gas and data are acquired.
FIG. 1 is a time-current curve of a solid-state anodization process of dilithium metal in an example. Typical metal anodization curves are shown and the current levels reach microampere levels, demonstrating the presence of ion transport in the transition solid electrolyte.
FIG. 2 is an SEM photograph of an in-situ protective film on a lithium metal surface prepared in the first and second embodiments;
lithium metal electrode stability test:
a Shenzhen New Willer battery test system is adopted to collect constant current charging and discharging data of the lithium cobaltate-lithium metal full battery, and the current is 1C multiplying power. The cut-off charge-discharge voltage range is 2.5-4.2V.
FIG. 3 is a graph showing cycle comparison of a bare lithium/lithium cobaltate full cell and a full cell of lithium metal and lithium cobaltate protected by an in-situ protective film prepared in example one and example two; wherein 1 is a cycle capacity curve of a bare lithium/lithium cobaltate full battery; 2 is the cycle capacity curve of the protected lithium/lithium cobaltate full cell prepared in example one and example two; 3 is the protected lithium/lithium cobaltate full cell coulombic efficiency change curve prepared in the first and second examples; and 4, a change curve of the efficiency of the naked lithium/lithium cobaltate full battery coulombs. As can be seen from fig. 3, the bare lithium/lithium cobaltate full cell failed immediately after 76 cycles, due to the inability of the cell to complete normal charging and discharging behavior due to micro-shorting caused by the large amount of lithium dendrites. The lithium metal/lithium cobaltate full battery protected by the in-situ film can effectively circulate for 300 circles, and the coulombic efficiency is kept above 99.5%, which indicates that the lithium dendrite is well inhibited.
FIG. 4 is a comparison graph of XPS test results of an in-situ protective film protected lithium metal surface and a bare lithium surface prepared in example one and example two; wherein 1, the C1s spectrum of the protected lithium surface prepared in the first embodiment and the second embodiment, and 2, the C1s spectrum of the naked lithium surface. It can be seen from the figure that the bare lithium surface is mainly Li caused by the ambient atmosphere2CO3And the protected lithium is a carbon-rich lithium compound, which shows that organic matters remained in the transition solid electrolyte can be decomposed into carbon compound negative ions under voltage and move to the surface of lithium metal to be combined with lithium ions generated at the anode to form a protective layer.
FIG. 5 is a comparison of XPS test results for a fluorine-containing in-situ protective film protected lithium metal surface and a bare lithium surface formed by anodic oxidation of HFE prepared in example three; wherein 1 the spectrum of F1s for the protected lithium surface prepared in example three, and 2 is the spectrum of F1s for the bare lithium surface. It can be seen from the figure that the bare lithium surface has no obvious F element peak, while the protected lithium surface contains lithium fluoride, which shows that the hydrofluoroether dripped on the surface of the transition solid electrolyte decomposes into fluorine anions under voltage and moves to the lithium metal surface and the protective layer containing lithium fluoride generated at the anode.
FIG. 6 is a graph showing the cycle charge and discharge test of a full cell comprising lithium metal and lithium cobaltate protected by a fluorine-containing in-situ protective film formed by the anodic oxidation of HFE prepared in example III; it can be seen from the figure that when the protective layer contains lithium fluoride, the battery can effectively cycle for at least 400 cycles, and the stability of the lithium metal negative electrode is greatly improved.
The stability of the lithium metal electrode in charge-discharge cycles is an important index for measuring the performance of the lithium metal electrode, and the results show that the in-situ protective film prepared by the solid-state anodic oxidation technology has a remarkable protection effect on the lithium metal electrode with poor stability, and can well inhibit the growth of lithium dendrites. The protective film based on the solid anodic oxidation technology provided by the invention has the functions of homogenizing lithium ion flow and eliminating/inhibiting the growth of lithium dendrites.
Claims (8)
1. The method for protecting the lithium metal negative electrode by in-situ film forming is characterized by comprising the following steps of:
firstly, preparing a transition electrolyte membrane:
a. adding isopropanol aluminum powder into an ethylene glycol ethyl ether solvent, performing ultrasonic dispersion uniformly to obtain a mixed solution, stirring for 20-40 minutes at 60-80 ℃, then adding an acetylacetone complexing agent, continuing to perform stirring reaction at 60-80 ℃, finally adding glacial acetic acid, performing stirring reaction for 20-40 minutes at 100-120 ℃, cooling to room temperature, and filtering to obtain an alumina precursor sol;
b. spin coating the alumina precursor sol on a conductive substrate, heating and curing, and repeating spin coating and heating and curing for multiple times to obtain an alumina film;
c. placing the alumina film in a muffle furnace, heating to 630-680 ℃ at the speed of 1 ℃/min, preserving heat, and naturally cooling to room temperature to obtain a conductive substrate loaded with a transition solid electrolyte film;
secondly, preparing the metal electrode protected by the in-situ film:
polishing a metal material, placing the polished metal material on a conductive substrate loaded with a transition solid electrolyte membrane under the protection of argon, clamping and then respectively applying negative voltage and positive voltage to the conductive substrate and the metal material, and carrying out anodic oxidation treatment, namely obtaining an in-situ protective membrane on the surface of the metal material;
and c, dripping a protective film component regulating and controlling solution on the conductive substrate loaded with the transition solid electrolyte film, wherein the protective film component regulating and controlling solution is one or more of a lithium difluorophosphate solution, a lithium nitrate solution and a LiFSI solution.
2. The method for protecting the lithium metal negative electrode by in-situ film formation according to claim 1, wherein a nano powder material is further added into the alumina precursor sol in the step a, wherein the nano powder material is MoO3Nano powder, ZnO nano powder, TiO2Nano powder, NiO nano powder, Ni2O3Nano powder and Al2O3Nano powder and Bi2O3Nano powder, ZnFe2O4Nano powder or CuBi2O4And (3) nano powder.
3. The method for in-situ film formation and protection of the lithium metal negative electrode according to claim 2, wherein the preparation method of the ZnO nano powder is as follows: weighing 2 parts of zinc nitrate and 1 part of sodium hydroxide according to the parts by weight, mixing and grinding the zinc nitrate and the sodium hydroxide for 20-50 min to obtain precursor slurry; and annealing the precursor slurry at the temperature of 250 ℃ to obtain ZnO nanorod powder.
4. The method for protecting the lithium metal negative electrode through in-situ film forming according to claim 2, wherein the nano powder material is added into the mixed solution, and the concentration of the nano powder material in the mixed solution is 10-50 mmol/L.
5. The method for protecting the lithium metal negative electrode by in-situ film formation according to claim 1, wherein in the step b, an alumina precursor sol is spin-coated on the conductive substrate by a spin coater, and the rotation speed of the spin coater is controlled to be 1000-3000 rpm.
6. The method for protecting the lithium metal cathode through in-situ film formation according to claim 1, wherein the thickness of the transition solid electrolyte film on the conductive substrate in the step c is 0.1-30 μm.
7. The method for protecting lithium metal negative electrode according to claim 1, wherein the conductive substrate in the second step is a silicon wafer, a platinum sheet, an aluminum sheet or a gold-plated sheet.
8. The method for protecting the lithium metal negative electrode according to claim 1, wherein the thickness of the in-situ protective film in the second step is 1 to 20 μm.
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