CN115566198A - Three-dimensional current collector with functional protective layer, lithium metal composite electrode and application - Google Patents
Three-dimensional current collector with functional protective layer, lithium metal composite electrode and application Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
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- H01M4/00—Electrodes
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Abstract
The application discloses a three-dimensional current collector with a functional protective layer, a lithium metal composite electrode and application, wherein the three-dimensional current collector with the functional protective layer comprises a three-dimensional current collector and a functional protective layer; the functional protective layer is coated on the surface of the three-dimensional current collector; the functional protective layer comprises one or more of silver, gold, magnesium, aluminum, zinc, tin, gallium, copper, aluminum oxide, zinc oxide, magnesium oxide, tin dioxide, vanadium pentoxide, niobium pentoxide, tantalum pentoxide, copper oxide, molybdenum trioxide and zirconium oxide. After the three-dimensional current collector with the functional protective layer and the lithium metal form the composite electrode, the transmission rate of lithium ions can be increased, electrons can be prevented from escaping to the surface of the electrode to attack electrolyte to cause capacity attenuation of the battery at the initial cycle stage, and therefore the regulation and control effect is achieved in the lithium metal deposition process.
Description
Technical Field
The application relates to a three-dimensional current collector with a functional protective layer, a lithium metal composite electrode and application, and belongs to the field of lithium metal batteries.
Background
Energy is a key global problem and is undoubtedly one of the most interesting topics in modern science and technology. Fossil fuels account for over 80% of the world's primary energy consumption, causing air and water pollution, the greenhouse effect of carbon dioxide emissions, and other serious environmental problems. In 2015, 195 countries signed a promise in paris to reduce greenhouse gas emissions, suggesting that energy shortage is an urgent and compelling problem to be solved. Therefore, the exploration of new materials and innovative energy conversion strategies are of great importance. In this case, the secondary energy storage device comes into the field of vision of people. Lithium batteries are the first to come, especially Lithium Ion Batteries (LIBs) and Lithium Metal Batteries (LMBs) which are highly portable. Lithium ion batteries have not achieved their full application prospects: the theoretical specific capacity of the graphite cathode is low (372 mAh g) -1 ) The requirements of large-scale energy storage equipment on high energy density and high power in the modern times cannot be met.
The theoretical specific capacity of the lithium metal negative electrode in a lithium metal battery is high (3860 mAh g) -1 ) And simultaneously has lower electrode potential (-3.04V vs RHE), and is considered to be one of the most ideal cathode materials. However, the problems that exist are not negligible: lithium dendrites are easily formed on the lithium metal negative electrode in the lithium deposition/stripping process, and the diaphragm can be pierced by the uncontrollable growth of the lithium dendrites, so that thermal runaway is caused when the battery is short-circuited, and the safety problem is caused. And in all-solid batteries, the poor contact with the electrodes and generally low conductivity due to the inherent rigidity and brittleness of the solid electrolyte allow the battery to rapidly fade in capacity during cycling. In order to solve the above problems, researchers have conducted extensive research on artificial functional oxide layer three-dimensional current collectors and composite electrodes.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method and application of a lithium metal composite electrode with excellent performance. A functional oxide protective layer is uniformly coated on a three-dimensional framework of a three-dimensional current collector, and then the functional oxide protective layer and lithium metal form a lithium metal composite electrode together. The three-dimensional current collector has a large specific surface area, is coated by a uniform and compact functional protective layer, and can accelerate the transmission rate of lithium ions and prevent electrons from escaping to the surface of an electrode to attack electrolyte to cause capacity attenuation of a battery at the initial cycle stage after forming a composite electrode with lithium metal, thereby playing a role in regulation and control in the deposition process of the lithium metal. The functional oxide protective layer undergoes lithiation at the initial stage of the cycle of the all-solid battery, is sufficiently coupled with the three-dimensional skeleton, and stably achieves lithium deposition and exfoliation in the subsequent charge and discharge processes, thereby exhibiting excellent cycle stability.
According to a first aspect of the present application, there is provided a three-dimensional current collector with a functional protection layer, comprising a three-dimensional current collector and a functional protection layer;
the functional protective layer is coated on the surface of the three-dimensional current collector;
the functional protective layer comprises one or more of silver, gold, magnesium, aluminum, zinc, tin, gallium, copper, aluminum oxide, zinc oxide, magnesium oxide, tin dioxide, vanadium pentoxide, niobium pentoxide, tantalum pentoxide, copper oxide, molybdenum trioxide and zirconium oxide.
Optionally, the functional protective layer is one or more layers.
Optionally, the functional protective layer has a thickness of 10nm to 10 μm.
Optionally, the upper limit of the thickness of the functional protective layer is independently selected from 10 μm, 6 μm, 2 μm, 1 μm, 0.5 μm, 0.1 μm, 0.05 μm, and the lower limit is independently selected from 0.01 μm, 6 μm, 2 μm, 1 μm, 0.5 μm, 0.1 μm, 0.05 μm.
The application provides a functional protective layer and a selectable three-dimensional current collector that contain that different kinds of metallic element constitute, wherein functional protective layer can be made by multiple method, simultaneously with multiple the functional protective layer is according to the difference cladding in proper order of kind or brush on the three-dimensional current collector on the conductive network, and after fully drying, the protective layer is even and the compact cladding in the surface of three-dimensional current collector, obtains the three-dimensional current collector that has functional protective layer.
Optionally, the functional protective layer comprises three layers; vanadium pentoxide, niobium pentoxide and tantalum pentoxide are sequentially arranged from inside to outside.
Optionally, the three-dimensional current collector is selected from one or more of copper foil, copper foam, aluminum foil, nickel foam, stainless steel, conductive resin, polyethylene-based composite conductive material, graphene, titanium-nickel memory alloy, carbon paper and carbon fiber.
Optionally, the stainless steel is porous stainless steel.
Preferably, the three-dimensional current collector is selected from carbon paper three-dimensional current collectors.
Optionally, the thickness of the three-dimensional current collector is 20 μm to 250 μm.
Optionally, the upper thickness limit of the three-dimensional current collector is independently selected from 250 μm, 200 μm, 150 μm, 100 μm, 50 μm, 30 μm, and the lower thickness limit is independently selected from 20 μm, 200 μm, 150 μm, 100 μm, 50 μm, 30 μm.
According to a second aspect of the present application, there is provided a method for preparing the above three-dimensional current collector with a functional protection layer, the method comprising:
and coating a functional protective layer source material on the surface of the three-dimensional current collector, and optionally performing a sintering step to obtain the three-dimensional current collector with the functional protective layer.
Optionally, the coating is selected from any one of the following methods: solvothermal methods, electrostatic spinning methods, solution methods, pulsed laser deposition, chemical vapor deposition, sol-gel methods, hydrothermal methods, magnetron sputtering methods, electroplating methods, chemical dip coating methods, vacuum evaporation methods, ion-beam sputtering methods.
Alternatively, the conditions of the hydrothermal process: the temperature is 120-220 ℃, and the time is 10-24h; conditions of the solvothermal method: the temperature is 100-250 ℃, and the time is 10-24h; conditions of the electrospinning method: the temperature is 20-40 ℃, and the time is 5-10h; conditions of the solution method: the temperature is 25 ℃, the time is 2 hours, and the protective atmosphere is argon; conditions of the magnetron sputtering method: the temperature is 25 ℃, the time is 6 hours, and the protective atmosphere is vacuum; conditions of the sol-gel method: the temperature is 25 ℃, and the time is 5h; conditions of the plating method: the temperature is 25 ℃, and the time is 2h; conditions of the vacuum deposition method: the temperature is 1500 ℃, and the protective atmosphere is vacuum.
Optionally, the conditions of the hydrothermal process are: the temperature is 120-220 ℃; the time is 10-24h.
Alternatively, the hydrothermal process has an upper temperature limit independently selected from 220 ℃, 200 ℃, 180 ℃, 160 ℃, 140 ℃ and a lower temperature limit independently selected from 120 ℃, 200 ℃, 180 ℃, 160 ℃, 140 ℃. The upper time limit is independently selected from 24h, 20h, 16h and 12h, and the lower time limit is independently selected from 10h, 20h, 16h and 12h.
Optionally, the preparation method is a hydrothermal method, the total volume of the solution participating in the reaction is less than 3/5 of the volume of the inner lining of the reaction kettle, and the volume of the inner lining of the reaction kettle is 50-100ml.
Optionally, the functional protection layer source material is at least one selected from a silver target, jin Bacai, a magnesium target, a gallium target, an aluminum foil, a zinc sheet, a tin foil, aluminum oxide, zinc oxide, magnesium oxide, tin dioxide, copper oxide, molybdenum disulfide, zirconium oxide, ammonium metavanadate, niobium oxalate, tantalum pentachloride, and a copper foil.
According to a third aspect of the present application, there is provided a lithium metal composite electrode comprising a three-dimensional current collector having a functional protective layer and metallic lithium;
the three-dimensional current collector with the functional protective layer is coated on the surface of the metal lithium;
the three-dimensional current collector with the functional protection layer is selected from the three-dimensional current collectors with the functional protection layers.
According to a fourth aspect of the present application, there is provided a method of preparing the above lithium metal composite electrode, the method comprising: and contacting the three-dimensional current collector with the functional protective layer with metal lithium, and applying pressure to obtain the lithium metal composite electrode.
According to a fifth aspect of the present application, there is provided a lithium metal battery comprising a positive electrode, a negative electrode and an electrolyte, the negative electrode employing the above-described lithium metal composite electrode.
Optionally, the lithium metal battery is a lithium metal all-solid-state battery or a lithium metal liquid battery.
The beneficial effects that this application can produce include:
(1) The current collector is a three-dimensional current collector with a functional protective layer, and through a high-temperature and high-pressure hydrothermal reaction, the oxides can be uniformly and densely coated on the surface of the current collector;
(2) The functional protective layer can not only accelerate the transmission rate of lithium ions, but also prevent electrons from escaping to the surface of an electrode to attack electrolyte to cause capacity attenuation in the charge-discharge cycle process of the battery, thereby playing a role in regulation and control in the lithium metal deposition process;
(3) The functional protective layer is lithiated at the initial stage of the cycle of the all-solid-state battery and is fully coupled with the three-dimensional framework, and stable lithium deposition and stripping can be realized in the battery cycle process, so that the cycle stability of the battery is improved, and the coulomb efficiency of the battery is improved.
Drawings
FIG. 1 is a graph of capacity and coulombic efficiency at 0.1C cycle rate for lithium metal all-solid-state batteries of example 1 and comparative example 1, with protective layer V 2 O 5 Prepared by a hydrothermal method;
FIG. 2 is a graph of capacity and coulombic efficiency at 0.1C cycle rate for lithium metal all-solid-state batteries of example 2 and comparative example 1, with the protective layer being Nb 2 O 5 Prepared by a hydrothermal method;
FIG. 3 is a graph of capacity and coulombic efficiency at 0.1C cycle rate for lithium metal all solid-state batteries of example 3 and comparative example 1, with protective layer V 2 O 5 Prepared by a hydrothermal method;
FIG. 4 is a plot of the specific capacity and voltage at 0.1C cycle rate for an assembled lithium metal hydride solid state battery of example 4 with a protective layer of V 2 O 5 Prepared by a hydrothermal method;
FIG. 5 is a plot of the specific capacity and voltage at 0.1C cycle rate for an assembled lithium metal liquid solid state battery of example 5 with a protective layer of Nb 2 O 5 Prepared by a hydrothermal method;
FIG. 6 is a plot of specific capacity and voltage at 0.1C cycle rate for an assembled lithium metal hydride solid state battery of example 6 with a protective layer of Ta 2 O 5 Prepared by a hydrothermal method;
FIG. 7 is a plot of the specific capacity and voltage at 0.1C cycle rate for an assembled lithium metal all-solid-state battery of example 7 with multiple layers of protective layers, V in that order 2 O 5 、Nb 2 O 5 、Ta 2 O 5 ；
Fig. 8 is a plot of the specific capacity and voltage at 0.1C cycle rate for an assembled lithium metal all-solid-state battery of example 8, in which an Ag protective layer was made by magnetron sputtering;
fig. 9 is a graph of the specific capacity and voltage at 0.1C cycle rate for an assembled lithium metal all solid state battery of example 9 in which an Au protective layer was formed by a magnetron sputtering process;
fig. 10 is a plot of the specific capacity and voltage at 0.1C cycle rate for an assembled lithium metal all-solid-state battery of example 10, with a Mg protective layer made by magnetron sputtering;
FIG. 11 is a plot of specific capacity and voltage at 0.1C cycle rate for an assembled lithium metal all solid state battery of example 11 with Al 2 O 3 The protective layer is prepared by an electrostatic spinning method;
fig. 12 is a plot of the specific capacity and voltage at 0.1C cycle rate for an assembled lithium metal all-solid-state battery of example 12, in which a ZnO protective layer was made by an electrospinning process;
fig. 13 is a graph of the specific capacity and voltage at 0.1C cycle rate for an assembled lithium metal all-solid-state battery of example 13 in which an MgO protective layer was fabricated by an electrospinning method;
fig. 14 is a plot of specific capacity and voltage at 0.1C cycle rate for an assembled lithium metal all solid state battery of example 14, with a Cu protective layer made by vacuum evaporation.
Detailed Description
The present application is described in detail below with reference to embodiments, and many specific details are set forth in the following description in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those described herein, and therefore the scope of the present invention is not limited by the specific embodiments disclosed below.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; materials used in the following examples, and the like, unless otherwise specified, raw materials in the examples of the present application were all purchased from commercial sources; the instruments used in the following examples, unless otherwise specified, were set to the manufacturer's recommended parameters.
Comparative example 1
And (3) forming a composite electrode by the pure carbon paper current collector without any modification and the lithium metal, and assembling the lithium metal all-solid-state battery. The result is shown in FIG. 1, and the specific discharge capacity of the first turn is 127.2mAh g -1 The coulombic efficiency of the first cycle is 92.1%, and the capacity retention rate of 200 cycles of charge and discharge is 48.4%.
Comparative example 2
And (3) forming a composite electrode by the pure carbon paper current collector without any modification and the lithium metal, and assembling the lithium metal liquid battery. The results are shown in Table 2, and the specific discharge capacity of the first coil was 137.5mAh g -1 The first turn of coulombic efficiency is 70.4 percent, and the capacity retention rate of 100 turns of charge-discharge cycle is 67.3 percent
Example 1
Preparation of V-containing compound according to the following procedure 2 O 5 And (3) modifying the composite electrode of the carbon paper current collector, and assembling the lithium metal all-solid-state battery, wherein the thickness of the protective layer is 300nm. The result is shown in FIG. 1, and the specific discharge capacity of the first loop is 128.8mAh g -1 The coulombic efficiency of the first cycle is 94.6%, and the capacity retention rate of 200 cycles of charge-discharge cycles is 91.2%. The preparation steps are as follows:
(1) Sequentially ultrasonically cleaning a carbon paper three-dimensional current collector in deionized water and absolute ethyl alcohol respectively, and then drying;
(2) Adding 0.4g of ammonium metavanadate into a certain amount of deionized water/absolute ethyl alcohol/concentrated nitric acid mixed solution, wherein 20mL of deionized water, 10mL of absolute ethyl alcohol and 5mL of concentrated nitric acid are heated and stirred at a constant temperature of 60 ℃ to obtain golden precursor solution (I);
(3) Placing the precursor solution (I) obtained in the step (2) and the carbon paper three-dimensional current collector obtained in the step (1) into a hydrothermal reaction kettle, and controlling the reaction temperatureThe temperature and the time are 180 ℃ and the time is 12 hours to obtain V 2 O 5 Modifying a carbon paper current collector by using a precursor;
(4) V obtained in the step (3) 2 O 5 Taking out the precursor modified carbon paper current collector, sequentially cleaning the carbon paper current collector with deionized water and absolute ethyl alcohol, and drying the carbon paper current collector;
(5) V obtained in the step (4) 2 O 5 Putting the precursor modified carbon paper current collector into a muffle furnace, and sintering by controlling the temperature and time to ensure that V is 2 O 5 Conversion of precursor to V 2 O 5 At 400 ℃ for 1 hour to obtain V 2 O 5 Modifying a carbon paper current collector;
(6) V obtained in the step (5) 2 O 5 And forming a composite electrode by the modified carbon paper current collector and the lithium metal, and assembling the lithium metal all-solid-state battery.
Example 2
Nb-containing alloy is prepared according to the following steps 2 O 5 And (3) modifying the composite electrode of the carbon paper current collector, and assembling the lithium metal all-solid-state battery, wherein the thickness of the protective layer is 350nm. The results are shown in FIG. 2, where the first-turn specific discharge capacity was 127.7mAh g -1 The coulombic efficiency of the first cycle is 93.6%, and the capacity retention rate of 100 cycles of charge and discharge cycles is 93.6%. The preparation steps are as follows:
(1) Adding 0.15g of niobium oxalate and hexamethylenetetramine into a deionized water/absolute ethyl alcohol mixed solution, wherein the deionized water is 20mL, the absolute ethyl alcohol is 10mL, and heating and stirring at a constant temperature of 60 ℃ to obtain a transparent clear precursor solution (II);
(2) Placing the precursor liquid (II) obtained in the step (1) and a carbon paper three-dimensional current collector in a hydrothermal reaction kettle, controlling the reaction temperature and the reaction time, controlling the temperature to be 180 ℃ and the reaction time to be 12 hours to obtain Nb 2 O 5 Modifying a carbon paper current collector by using a precursor;
(3) Nb obtained in the step (2) 2 O 5 Taking out the precursor modified carbon paper current collector, sequentially cleaning the carbon paper current collector with deionized water and absolute ethyl alcohol, and drying the carbon paper current collector;
(4) Under inert atmosphere, nb obtained in the step (3) is added 2 O 5 Putting the precursor modified carbon paper current collector into a tubeFurnace, controlling temperature and time to sinter to obtain Nb 2 O 5 Conversion of precursors to Nb 2 O 5 At 700 ℃ for 3 hours to obtain Nb 2 O 5 Modifying a carbon paper current collector;
(5) Nb obtained in the step (4) 2 O 5 And forming a composite electrode by the modified carbon paper current collector and the lithium metal, and assembling the lithium metal all-solid-state battery.
Example 3
Ta-containing compounds were prepared according to the following procedure 2 O 5 And (3) modifying the composite electrode of the carbon paper current collector, and assembling the lithium metal all-solid-state battery, wherein the thickness of the protective layer is 200nm. The result is shown in FIG. 3, where the first-turn specific discharge capacity was 141.5mAh g -1 The coulombic efficiency of the first cycle is 93.7%, and the capacity retention rate of 100 cycles of charge-discharge cycle is 92.6%. The preparation steps are as follows:
(1) Adding 0.46g of tantalum pentachloride into a certain amount of absolute ethyl alcohol/polyethylene glycol/deionized water mixed solution, wherein 20mL of absolute ethyl alcohol, 5mL of polyethylene glycol and 1mL of deionized water are heated and stirred at a constant temperature of 60 ℃ to obtain a transparent clear precursor solution (III);
(2) Placing the precursor liquid (III) obtained in the step (1) and a carbon paper three-dimensional current collector in a hydrothermal reaction kettle, controlling the reaction temperature and the reaction time to 200 ℃ for 24 hours to obtain Ta 2 O 5 Modifying a carbon paper current collector by using the precursor;
(3) Subjecting Ta obtained in the step (2) to 2 O 5 Taking out the precursor modified carbon paper current collector, sequentially cleaning the carbon paper current collector with deionized water and absolute ethyl alcohol, and drying the carbon paper current collector;
(4) In an inert atmosphere, adding Ta obtained in the step (3) 2 O 5 Putting the precursor modified carbon paper current collector into a tube furnace, and sintering at controlled temperature and time to obtain Ta 2 O 5 Conversion of precursor to Ta 2 O 5 At 800 deg.C for 3 hours to obtain Ta 2 O 5 Modifying a carbon paper current collector;
(5) Ta obtained in the step (4) 2 O 5 And forming a composite electrode by the modified carbon paper current collector and the lithium metal, and assembling the lithium metal all-solid-state battery.
Example 4
Preparation of a composition containing V according to the following procedure 2 O 5 And (3) modifying the composite electrode of the carbon paper current collector, and assembling the lithium metal liquid battery, wherein the thickness of the protective layer is 300nm. The results are shown in FIG. 4, in which the first-turn specific discharge capacity was 157.0mAh g -1 The coulombic efficiency of the first cycle is 87.3%, and the capacity retention rate of 100 cycles of charge-discharge cycle is 82.1%. The preparation steps are as follows:
(1) Sequentially ultrasonically cleaning a carbon paper three-dimensional current collector in deionized water and absolute ethyl alcohol respectively, and then drying;
(2) Adding 0.4g of ammonium metavanadate into a certain amount of deionized water/absolute ethyl alcohol/concentrated nitric acid mixed solution, wherein 20mL of deionized water, 10mL of absolute ethyl alcohol and 5mL of concentrated nitric acid are heated and stirred at a constant temperature of 60 ℃ to obtain golden precursor solution (I);
(3) Placing the precursor solution (I) obtained in the step (2) and the carbon paper three-dimensional current collector obtained in the step (1) in a hydrothermal reaction kettle, controlling the reaction temperature and the reaction time, controlling the temperature to be 180 ℃ and the reaction time to be 12 hours to obtain V 2 O 5 Modifying a carbon paper current collector by using a precursor;
(4) V obtained in the step (3) 2 O 5 Taking out the precursor modified carbon paper current collector, sequentially cleaning the precursor modified carbon paper current collector by using deionized water and absolute ethyl alcohol, and then drying the precursor modified carbon paper current collector;
(5) V obtained in the step (4) 2 O 5 Putting the precursor modified carbon paper current collector into a muffle furnace, and sintering by controlling the temperature and time to ensure that V 2 O 5 Conversion of precursor to V 2 O 5 At 400 ℃ for 1 hour to obtain V 2 O 5 Modifying a carbon paper current collector;
(6) V obtained in the step (5) 2 O 5 And forming a composite electrode by the modified carbon paper current collector and the lithium metal, and assembling the lithium metal liquid battery.
Example 5
Nb content was prepared according to the following procedure 2 O 5 And (3) modifying the composite electrode of the carbon paper current collector, and assembling the lithium metal liquid battery, wherein the thickness of the protective layer is 350nm. The result is shown in FIG. 5, and the first-turn specific discharge capacity is 149.9mAh g -1 The coulombic efficiency of the first cycle is 89.5%, and the capacity retention rate of 100 cycles of charge-discharge cycle is 83.8%. The preparation steps are as follows:
(1) Adding 0.15g of niobium oxalate and hexamethylenetetramine into a deionized water/absolute ethyl alcohol mixed solution, wherein the deionized water is 20mL, the absolute ethyl alcohol is 10mL, and heating and stirring at a constant temperature of 60 ℃ to obtain a transparent clear precursor solution (II);
(2) Placing the precursor liquid (II) obtained in the step (1) and a carbon paper three-dimensional current collector in a hydrothermal reaction kettle, controlling the reaction temperature and the reaction time, controlling the temperature to be 180 ℃ and the reaction time to be 12 hours to obtain Nb 2 O 5 Modifying a carbon paper current collector by using a precursor;
(3) Nb obtained in the step (2) 2 O 5 Taking out the precursor modified carbon paper current collector, sequentially cleaning the carbon paper current collector with deionized water and absolute ethyl alcohol, and drying the carbon paper current collector;
(4) Under inert atmosphere, nb obtained in the step (3) is added 2 O 5 Putting the precursor modified carbon paper current collector into a tube furnace, and sintering by controlling the temperature and time to ensure that the Nb is 2 O 5 Conversion of precursors to Nb 2 O 5 At 700 ℃ for 3 hours to obtain Nb 2 O 5 Modifying a carbon paper current collector;
(5) Nb obtained in the step (4) 2 O 5 And forming a composite electrode by the modified carbon paper current collector and the lithium metal, and assembling the lithium metal liquid battery.
Example 6
Ta-containing compounds were prepared according to the following procedure 2 O 5 And (3) modifying the composite electrode of the carbon paper current collector, and assembling the lithium metal liquid battery, wherein the thickness of the protective layer is 200nm. The result is shown in FIG. 6, where the first-turn specific discharge capacity was 153.1mAh g -1 The coulombic efficiency of the first cycle is 77.8%, and the capacity retention rate of 100 cycles of charge-discharge cycle is 82.0%. The preparation steps are as follows:
(1) Adding 0.46g of tantalum pentachloride into a certain amount of absolute ethyl alcohol/polyethylene glycol/deionized water mixed solution, wherein 20mL of absolute ethyl alcohol, 5mL of polyethylene glycol and 1mL of deionized water are heated and stirred at a constant temperature of 60 ℃ to obtain a transparent clear precursor solution (III);
(2) Will be described in detail(1) Placing the obtained precursor liquid (III) and a carbon paper three-dimensional current collector in a hydrothermal reaction kettle, controlling the reaction temperature and time to 200 ℃ and 24 hours to obtain Ta 2 O 5 Modifying a carbon paper current collector by using a precursor;
(3) Subjecting Ta obtained in the step (2) to 2 O 5 Taking out the precursor modified carbon paper current collector, sequentially cleaning the carbon paper current collector with deionized water and absolute ethyl alcohol, and drying the carbon paper current collector;
(4) In an inert atmosphere, adding Ta obtained in the step (3) 2 O 5 Putting the precursor modified carbon paper current collector into a tube furnace, controlling the temperature and the time to sinter to obtain Ta 2 O 5 Conversion of precursor to Ta 2 O 5 At 800 deg.C for 3 hours to obtain Ta 2 O 5 Modifying a carbon paper current collector;
(5) Ta obtained in the step (4) 2 O 5 And forming a composite electrode by the modified carbon paper current collector and the lithium metal, and assembling the lithium metal liquid battery.
Example 7
Preparing a composite electrode containing a carbon paper current collector modified by a plurality of protective layers according to the following steps, wherein the plurality of protective layers are V in sequence 2 O 5 、Nb 2 O 5 、Ta 2 O 5 A lithium metal all-solid-state battery was assembled in which the total thickness of the protective layer was 700nm. The result is shown in FIG. 7, where the first charge specific capacity is 136.2mAh g -1 The first circle discharge specific capacity is 128.8mAh g -1 The preparation method comprises the following steps:
(1) Adding 0.4g of ammonium metavanadate into a certain amount of deionized water/absolute ethyl alcohol/concentrated nitric acid mixed solution, wherein the deionized water is 20mL, the absolute ethyl alcohol is 10mL, and the concentrated nitric acid is 5mL, so as to obtain golden yellow precursor solution (I); adding 0.15g of niobium oxalate and hexamethylenetetramine into a deionized water/absolute ethyl alcohol mixed solution, wherein the deionized water is 20mL, and the absolute ethyl alcohol is 10mL, so as to obtain a transparent clear precursor solution (II); adding 0.46g of tantalum pentachloride into a certain amount of absolute ethyl alcohol/polyethylene glycol/deionized water mixed solution, wherein 20mL of absolute ethyl alcohol, 5mL of polyethylene glycol and 1mL of deionized water are used to obtain a transparent clear precursor solution (III);
(2) Placing the precursor solution obtained in the step (1) and a carbon paper three-dimensional current collector in a hydrothermal reaction kettle in sequence, and controlling the reaction temperature and the reaction time, wherein the temperature is 180 ℃, 180 ℃ and 200 ℃, and the reaction time is 12 hours, 12 hours and 24 hours, so as to obtain three precursors which modify the carbon paper current collector together;
(3) Putting the three precursors obtained in the step (2) together modified carbon paper current collectors into a tube furnace under an inert atmosphere, controlling the temperature and the time to sinter, and respectively converting the precursors into V 2 O 5 、Nb 2 O 5 、Ta 2 O 5 The temperature is 800 ℃, the time is 3 hours, and a multi-layer protective layer is used for modifying the carbon paper current collector;
(4) And (4) forming a composite electrode by the multi-layer protective layer modified carbon paper current collector obtained in the step (3) and lithium metal, and assembling the lithium metal all-solid-state battery.
Example 8
The composite electrode containing the Ag nanolayer modified carbon paper current collector was prepared according to the following procedure, and a lithium metal all-solid-state battery was assembled, wherein the thickness of the protective layer was 50nm. The result is shown in FIG. 8, where the specific charge capacity of the first cycle is 138.0mAh g -1 The first circle discharge specific capacity is 127.2mAh g -1 The preparation method comprises the following steps:
(1) Sequentially ultrasonically cleaning a carbon paper three-dimensional current collector in deionized water and absolute ethyl alcohol respectively, and then drying;
(2) Fixing Ag target on sample base of vacuum chamber of magnetron sputtering system, setting magnetic field intensity of surface sputtering region to be 2800 gauss, setting distance from target to substrate to be 60mm, pumping vacuum chamber to 2 × 10 -3 Introducing argon after the pressure is lower than Pa so that the total pressure is kept at 0.8-1Pa;
(3) The sputtering power is set to be 50W, the substrate temperature is 400 ℃, and sputtering is started;
(4) The total sputtering time is 2h, after the sputtering is finished, a sample is removed from the vacuum chamber, a carbon paper current collector containing Ag nano-layer modification is obtained, then the composite electrode is formed with lithium metal, and the lithium metal all-solid-state battery is assembled.
Example 9
Preparing a composite electrode containing an Au nano-layer modified carbon paper current collector according to the following steps, and assembling lithiumMetal all-solid-state battery, wherein the protective layer thickness is 80nm. The result is shown in FIG. 9, where the first charge specific capacity is 125.6mAh g -1 And the first-circle discharge specific capacity is 121.0mAh g -1 The preparation method comprises the following steps:
(1) Sequentially ultrasonically cleaning a carbon paper three-dimensional current collector in deionized water and absolute ethyl alcohol respectively, and then drying;
(2) Fixing Au target on a sample base of a vacuum chamber of a magnetron sputtering system, setting the magnetic field intensity of a surface sputtering area to be 2400 gauss and the distance from the target to a substrate to be 60mm, pumping the vacuum chamber to 2 multiplied by 10 -3 Introducing argon after the pressure is lower than Pa so that the total pressure is kept at 0.8-1Pa;
(3) The sputtering power is set to be 60W, the temperature of the substrate is 400 ℃, and sputtering is started;
(4) The total sputtering time is 3h, after the sputtering is finished, a sample is removed from the vacuum chamber to obtain an Au-containing nano-layer modified carbon paper current collector, and then the Au-containing nano-layer modified carbon paper current collector and lithium metal form a composite electrode to assemble the lithium metal all-solid-state battery.
Example 10
Preparing a composite electrode of a Mg-containing layer modified carbon paper current collector according to the following steps, and assembling the lithium metal all-solid-state battery, wherein the thickness of the protective layer is 50nm. The results are shown in FIG. 10, in which the specific charge capacity of the first cycle was 89.7mAh g -1 The first circle discharge specific capacity is 86.8mAh g -1 The preparation method comprises the following steps:
(1) Sequentially ultrasonically cleaning a carbon paper three-dimensional current collector in deionized water and absolute ethyl alcohol respectively, and then drying;
(2) Fixing Mg target on a sample base of a vacuum chamber of a magnetron sputtering system, setting the magnetic field intensity of a surface sputtering area to be 2800 gauss, setting the distance from the target to a substrate to be 60mm, pumping the vacuum chamber to 2 multiplied by 10 -3 Introducing argon after the pressure is lower than Pa so that the total pressure is kept at 0.8-1Pa;
(3) The sputtering power is set to be 60W, the temperature of the substrate is 400 ℃, and sputtering is started;
(4) The total sputtering time is 2h, after the sputtering is finished, a sample is removed from the vacuum chamber, a Mg-containing nano layer modified carbon paper current collector is obtained, and then the Mg-containing nano layer modified carbon paper current collector and lithium metal form a composite electrode to assemble the lithium metal all-solid-state battery.
Example 11
Al-containing alloy prepared according to the following procedure 2 O 3 And modifying the composite electrode of the carbon paper current collector by the protective layer, and assembling the lithium metal all-solid-state battery, wherein the thickness of the protective layer is 50nm. The result is shown in FIG. 11, where the specific charge capacity of the first cycle was 113.1mAh g -1 The first circle discharge specific capacity is 112.7mAh g -1 The preparation method comprises the following steps:
(1) Preparing a spinning solution by taking aluminum isopropoxide as an aluminum source, PVA as a thickening agent, nitric acid as a catalyst and deionized water as a solvent;
(2) Wherein, 8g of aluminum isopropoxide, 2g of PVA, 0.2g of nitric acid and 20mL of deionized water are subjected to electrostatic spinning;
(3) Wherein the electrostatic spinning voltage is controlled to be 18.5kV, the sample injection speed is 1.2mL/h, the environmental humidity is 19 percent, and the environmental temperature is 30 ℃, so as to obtain an alumina precursor;
(4) And (3) placing the precursor in a muffle furnace, heating at the speed of 2 ℃/min, preserving the temperature for 2h at the temperature of 1000 ℃ to obtain an aluminum oxide film, forming a composite electrode with lithium metal, and assembling the lithium metal all-solid-state battery.
Example 12
Preparing a composite electrode containing a ZnO protective layer modified carbon paper current collector according to the following steps, and assembling the lithium metal all-solid-state battery, wherein the thickness of the protective layer is 50nm. The result is shown in FIG. 12, where the specific charge capacity of the first cycle is 111.3mAh g -1 The first circle discharge specific capacity is 112.7mAh g -1 The preparation method comprises the following steps:
(1) Preparing a spinning solution by using zinc isopropoxide as a zinc source, PVA as a thickening agent, sulfuric acid as a catalyst and deionized water as a solvent;
(2) Wherein, 8g of aluminum isopropoxide, 2g of PVA, 0.2g of sulfuric acid and 20mL of deionized water are subjected to electrostatic spinning;
(3) Wherein the electrostatic spinning voltage is controlled to be 18.5kV, the sample injection speed is 1.2mL/h, the environmental humidity is 19 percent, and the environmental temperature is 30 ℃, so as to obtain a zinc oxide precursor;
(4) And (3) placing the precursor in a muffle furnace, heating at the speed of 2 ℃/min, preserving the temperature for 2h at the temperature of 1000 ℃ to obtain a zinc oxide film, forming a composite electrode with lithium metal, and assembling the lithium metal all-solid-state battery.
Example 13
The composite electrode of the carbon paper current collector modified with the MgO protective layer was prepared according to the following procedure, and a lithium metal all-solid battery was assembled, wherein the thickness of the protective layer was 60nm. The result is shown in FIG. 13, where the specific charge capacity of the first cycle is 105.1mAh g -1 The first circle discharge specific capacity is 104.6mAh g -1 The preparation method comprises the following steps:
(1) Preparing spinning solution by taking magnesium isopropoxide as a magnesium source, PVA as a thickening agent, sulfuric acid as a catalyst and deionized water as a solvent;
(2) Wherein 16g of magnesium isopropoxide, 4g of PVA, 0.3g of sulfuric acid and 20mL of deionized water are subjected to electrostatic spinning;
(3) Wherein the electrostatic spinning voltage is controlled to be 18.5kV, the sample injection speed is 1.2mL/h, the environmental humidity is 19 percent, and the environmental temperature is 30 ℃, so as to obtain a zinc oxide precursor;
(4) And (3) placing the precursor in a muffle furnace, heating at the speed of 2 ℃/min, preserving the temperature for 2h at the temperature of 1000 ℃ to obtain a MgO protective layer-containing modified carbon paper current collector, forming a composite electrode with lithium metal, and assembling the lithium metal all-solid-state battery.
Example 14
Preparing a composite electrode containing a Cu protective layer modified carbon paper current collector according to the following steps, and assembling the lithium metal all-solid-state battery, wherein the thickness of the protective layer is 250nm. The result is shown in FIG. 14, where the specific charge capacity of the first cycle was 103.1mAh g -1 The first circle discharge specific capacity is 103.0mAh g -1 The preparation method comprises the following steps:
(1) Vacuumizing the evaporation chamber of vacuum ion evaporation equipment to a vacuum degree of 1 × 10 -5 After Pa, enabling the carbon paper current collector to pass through a copper plating roller, wherein the copper plating roller is provided with a temperature zone with the temperature of 45 ℃ and the length of the temperature zone is 12mm;
(2) Copper metal with the purity of 99.9 percent in an evaporation boat is evaporated at 1800 ℃, the concentration of copper steam is maintained to be 70mol/L, wherein the movement speed of a carbon paper current collector is 30m/min in the evaporation process;
(3) And (4) finishing evaporation to obtain a Cu-containing protective layer modified carbon paper current collector, forming a composite electrode with lithium metal, and assembling the lithium metal all-solid-state battery.
Electrochemical performance test
Assembling a full battery: comparative examples 1 and 2 used a composite electrode composed of a pure carbon paper current collector without any modification and lithium metal as a negative electrode; example 1 metallic lithium having a diameter of 10mm and a thickness of 80 μm and V were used 2 O 5 A composite electrode formed by modifying a carbon paper three-dimensional current collector is used as a negative electrode; example 2 metallic lithium and Nb with a diameter of 10mm and a thickness of 80 μm were used 2 O 5 A composite electrode formed by modifying a carbon paper three-dimensional current collector is used as a negative electrode; example 3 lithium metal and Ta with a diameter of 10mm and a thickness of 80 μm were used 2 O 5 A composite electrode formed by modifying a carbon paper three-dimensional current collector is used as a negative electrode; example 4 lithium metal having a diameter of 16mm and a thickness of 50 μm and V were used 2 O 5 A composite electrode formed by modifying a carbon paper three-dimensional current collector is used as a negative electrode; example 5 lithium metal having a diameter of 16mm and a thickness of 50 μm and Nb were used 2 O 5 A composite electrode formed by modifying a carbon paper three-dimensional current collector is used as a negative electrode; example 6 lithium metal having a diameter of 16mm and a thickness of 50 μm and Ta were used 2 O 5 And a composite electrode formed by modifying the carbon paper three-dimensional current collector is used as a negative electrode. The assembly process of the composite electrode comprises the following steps: and superposing the carbon paper current collector and the metal lithium together, and then applying certain pressure of about 20Mpa to ensure that the carbon paper current collector is fully contacted with the lithium metal to jointly form the composite electrode. Comparative example 1 and example 1, example 2, example 3 and L respectively 6 PS 5 A Cl solid electrolyte and a LiCoO2 positive electrode are jointly assembled to form the lithium metal all-solid-state battery; comparative example 2, example 4, example 5 and example 6 were used in combination with a carbonate electrolyte and LiNi, respectively 0.88 Co 0.09 Al 0.03 O 2 The positive electrodes are collectively assembled into a lithium metal liquid battery.
Lithium metal all-solid-state battery test conditions: setting the standing time to be 2h and the charge-discharge cut-off voltage to be 3.0-4.2V vs + And setting the circulation multiplying power to be 0.1C for circulation until the coulomb efficiency is subjected to unstable fluctuation, and ending the program.
Lithium metal liquid battery test conditions: the standing time is set to be 12h, and the charge-discharge cut-off voltage is 2.8-4.3V vs + And setting the circulation multiplying power to be 0.1C for circulation until the coulomb efficiency is subjected to unstable fluctuation, and ending the program.
And (3) testing results:
lithium metal all-solid-state battery: comparative example 1 the specific discharge capacity of the first coil was 127.2mAh g -1 The first turn of coulombic efficiency is 92.1%, the capacity retention rate of 100 turns of charge-discharge cycle is 65.4%, and the capacity retention rate of 200 turns of charge-discharge cycle is 48.4%; example 1 the specific discharge capacity of the first coil was 128.8mAh g -1 The first turn of coulombic efficiency is 94.6%, the capacity retention rate of 100 turns of charge-discharge cycle is 92.3%, and the capacity retention rate of 200 turns of charge-discharge cycle is 91.2%; example 2 the specific discharge capacity of the first coil was 127.7mAh g -1 The coulombic efficiency of the first circle is 93.6 percent, and the capacity retention rate of 100 circles of charge-discharge cycle is 93.6 percent; example 3 the specific discharge capacity of the first coil was 141.5mAh g -1 The coulombic efficiency of the first cycle is 93.7%, and the capacity retention rate of 100 cycles of charge and discharge is 92.6%.
The respective capacities and coulombic efficiencies of the lithium metal all-solid-state batteries of example 1, example 2, example 3, and comparative example 1 at 0.1C cycle rate are as follows in table 1.
TABLE 1
Lithium metal liquid battery: comparative example 2 the first-turn specific discharge capacity was 137.5mAh g -1 The first-turn coulombic efficiency is 70.4%, and the capacity retention rate of 100 charge-discharge cycles is 67.3%; example 4 the specific discharge capacity of the first coil was 157.0mAh g -1 The first-turn coulombic efficiency is 87.3%, and the capacity retention rate of 100 charge-discharge cycles is 82.1%; example 5 specific discharge capacity of the first coil was 149.9mAh g -1 The first turn of coulombic efficiency is 89.5%, and the capacity retention rate of 100 turns of charge-discharge cycle is 83.8%; example 6 the specific discharge capacity of the first coil was 153.1mAh g -1 The first turn coulombic efficiency was 77.8%, and the capacity retention rate was 82.0% for 100 cycles of charge-discharge cycle.
The respective capacities and coulombic efficiencies of the lithium metal liquid batteries of example 4, example 5, example 6, and comparative example 2 at 0.1C cycle rate are as follows in table 2.
TABLE 2
Lithium metal liquid batteries of examples 4, 5, and 6; the specific charge/discharge capacities of the lithium metal all-solid-state batteries of examples 7, 8, 9, 10, 11, 12, 13, and 14 at a cycle rate of 0.1C are shown in table 3 below.
TABLE 3
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. The three-dimensional current collector with the functional protection layer is characterized by comprising the three-dimensional current collector and the functional protection layer;
the functional protective layer is coated on the surface of the three-dimensional current collector;
the functional protective layer comprises one or more of silver, gold, magnesium, aluminum, zinc, tin, gallium, copper, aluminum oxide, zinc oxide, magnesium oxide, tin dioxide, vanadium pentoxide, niobium pentoxide, tantalum pentoxide, copper oxide, molybdenum trioxide and zirconium oxide.
2. The three-dimensional current collector with the functional protective layer according to claim 1, wherein the functional protective layer is one or more layers;
preferably, the total thickness of the functional protective layer is 10nm to 10 μm;
preferably, the functional protective layer comprises three layers; vanadium pentoxide, niobium pentoxide and tantalum pentoxide are sequentially arranged from inside to outside;
preferably, the three-dimensional current collector is selected from one or more of copper foil, copper foam, aluminum foil, nickel foam, stainless steel, conductive resin, polyethylene-based composite conductive material, graphene, titanium-nickel memory alloy, carbon paper and carbon fiber;
preferably, the thickness of the three-dimensional current collector is 20 μm to 250 μm.
3. The method for preparing a three-dimensional current collector with a functional protection layer according to claim 1 or 2, wherein the method comprises:
and coating a functional protective layer source material on the surface of the three-dimensional current collector, and optionally performing a sintering step to obtain the three-dimensional current collector with the functional protective layer.
4. The method of claim 3, wherein the coating is selected from any one of the following methods: solvothermal methods, electrospinning methods, solution methods, pulsed laser deposition, chemical vapor deposition, sol-gel methods, hydrothermal methods, magnetron sputtering methods, electroplating methods, chemical dip plating methods, vacuum evaporation methods, ion-beam sputtering methods.
5. The process according to claim 4, characterized in that the conditions of the hydrothermal process are: the temperature is 120-220 ℃, and the time is 10-24h; conditions of the solvothermal method: the temperature is 100-250 ℃, and the time is 10-24h; conditions of the electrospinning method: the temperature is 20-40 ℃, and the time is 5-10h; conditions of the solution method: the temperature is 25 ℃, the time is 2 hours, and the protective atmosphere is argon; conditions of the magnetron sputtering method: the temperature is 25 ℃, the time is 6 hours, and the protective atmosphere is vacuum; conditions of the sol-gel method: the temperature is 25 ℃, and the time is 5h; conditions of the plating method: the temperature is 25 ℃, and the time is 2h; conditions of the vacuum deposition method: the temperature is 1500 ℃, and the protective atmosphere is vacuum.
6. The method according to claim 3, wherein the functional protective layer source material is at least one selected from the group consisting of silver target material, jin Bacai, magnesium target material, gallium target material, aluminum foil, zinc sheet, tin foil, aluminum oxide, zinc oxide, magnesium oxide, tin dioxide, copper oxide, molybdenum disulfide, zirconium oxide, ammonium metavanadate, niobium oxalate, tantalum pentachloride, and copper foil.
7. A lithium metal composite electrode, comprising a three-dimensional current collector having a functional protective layer and metallic lithium;
the three-dimensional current collector with the functional protective layer is coated on the surface of the metal lithium;
the three-dimensional current collector with the functional protection layer is selected from the three-dimensional current collectors with the functional protection layers of claims 1 or 2.
8. The method of preparing a lithium metal composite electrode according to claim 7, comprising: and contacting the three-dimensional current collector with the functional protective layer with metal lithium, and applying pressure to obtain the lithium metal composite electrode.
9. A lithium metal battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the negative electrode employs the lithium metal composite electrode according to claim 7.
10. The lithium metal battery of claim 9, wherein the lithium metal battery is a lithium metal all solid state battery or a lithium metal liquid state battery.
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