CN111916682A - Composite metal lithium cathode, preparation method thereof and lithium battery - Google Patents
Composite metal lithium cathode, preparation method thereof and lithium battery Download PDFInfo
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H01M4/382—Lithium
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Abstract
The invention relates to a composite metal lithium negative electrode, a preparation method thereof and a lithium battery, wherein the preparation method of the composite metal lithium negative electrode comprises the following steps: preparing a porous film-shaped carbon layer; subjecting the porous film-like carbon layer to lithiation-philic treatment; compounding the metal lithium with the porous film-shaped carbon layer subjected to lithiation-philic treatment to obtain a composite metal lithium cathode; in the composite metal lithium cathode, the porous film-shaped carbon layer subjected to lithiation affinity treatment forms a lithium affinity carbon framework, and metal lithium precipitates are attached to the carbon framework to form a network channel for interconnecting and communicating lithium ions in the charging and discharging process. The composite lithium metal cathode of the invention does not use a cathode current collector, thus improving the content of the cathode metal lithium, and the volume change of the lithium metal cathode in the charging and discharging process can be greatly relieved due to the existence of the carbon skeleton, thereby improving the quality/volume energy density of the lithium battery, improving the cycle performance and the safety performance of the battery, and simultaneously the electrode has high specific surface area and can increase the multiplying power performance of the battery.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a composite metal lithium cathode, a preparation method thereof and a lithium battery.
Background
The secondary lithium battery is a battery system with the highest energy density in the current commercial batteries, is widely applied to the fields of consumer electronics, electric automobiles, large-scale energy storage and the like, and the market segments of the application field are gradually expanded, such as the fields of medical electronics, electric tools, unmanned aerial vehicles, data centers, national safety and the like, and the rapid development of different fields plays an important role in promoting the development of high-energy density batteries.
The metallic lithium is the lowest of the currently known materials due to its specific capacity of 3860mAh/g, deposition potential of-3.04V (relative to standard hydrogen electrode), and has smaller density of 0.534g/cm3Therefore, when the metal lithium is used as a battery negative electrode, the energy density of each battery system formed is the most significant. However, lithium metal as a negative electrode still has problems in many aspects such as safety, volume change, rate, cyclability, cost, etc. that are still far from commercial application. The safety of metallic lithium cathodes is most notable for the lithium dendrites that are easily formed by the lithium ions during deposition. As early as 80 years of the last century, after a large number of safety accidents occurred in the first commercialization of lithium metal negative electrodes by Moli company, failure analysis was carried out on batteries to find that lithium dendrite can pierce through a diaphragm to cause short circuit, and thermal runaway behavior of the batteries occurred. However, the safety of lithium metal is reflected in internal short circuit of lithium dendrite, and also in side reactions of lithium powder generated after multiple cycles or 'dead lithium' and electrolyte source, which continuously generate gas and heat, direct and violent reaction of lithium powder and air after leakage, thermal safety thermal runaway and other safety problems need to be deeply excavated.
The volume change of the metallic lithium cathode directly corresponds to the surface capacity of the battery, and theoretically 1mAh/cm2Corresponding to a thickness variation of about 4.85 μm and therefore a large volume variation during cycling, the higher the face volume the greater the volume variation. Volume change coupled with non-uniform deposition dissolution corresponds to constant cracking and heaviness of the Solid Electrolyte Interface (SEI) filmWhich reduces coulomb efficiency. On the electrical core layer, the volume change corresponds to the problems of encapsulation, electrode falling, electric contact loss and the like.
The rate property of the metal lithium cathode is directly related to the current density of the surface of the metal lithium cathode, and the general metal lithium cathode has more uneven deposition and dissolution behaviors under high current density, is easier to grow lithium dendrite and is pulverized. This is because the large current density reduces the "beach time", a lithium-poor layer is formed on the surface of the lithium metal negative electrode in a shorter time, so that the growth of lithium dendrites is advanced.
The cyclability of lithium metal negative electrodes has been studied more, and it is believed that the cycle of lithium metal is directly related to the coulombic efficiency, that is, it is closely related to the side reaction of the electrolyte or the electrolyte solution. Therefore, the electrolyte can be optimized, interface modification is adopted, and the method of utilizing solid electrolyte and the like is utilized to improve the cycle performance of the battery.
The cost of the lithium metal negative electrode is considered to be the cost per unit capacity and the cost of the lithium metal negative electrode that can maintain a long cycle. The cost of the lithium metal cathode in the battery can be reduced by large-scale preparation, reduction of the usage amount of the lithium metal and improvement of the cyclicity.
In summary, pure metallic lithium anodes are still important and far from being directly applied to industrialization.
Disclosure of Invention
The embodiment of the invention provides a composite lithium metal cathode, a preparation method thereof and a lithium battery. The application provides a preparation method of a composite metal lithium negative electrode material, which is low in price, simple and convenient to prepare and capable of being produced in a large scale.
In a first aspect, an embodiment of the present invention provides a method for preparing a lithium composite anode, including:
preparing a porous film-shaped carbon layer;
subjecting the porous film-like carbon layer to lithiation-philic treatment;
compounding the metal lithium with the porous film-shaped carbon layer subjected to lithiation-philic treatment to obtain a composite metal lithium cathode;
in the composite metal lithium cathode, the porous film-shaped carbon layer subjected to lithiation affinity treatment forms a lithium affinity carbon framework, and metal lithium precipitates are attached to the carbon framework to form a network channel for interconnecting and communicating lithium ions in the charging and discharging process.
Preferably, the porous film-like carbon layer is composed of a graphite-like carbon material, an amorphous carbon-like material and/or a graphene-like carbon material;
the porous film-like carbon layer has a thickness of 20 to 200 μm and a porosity of 20 to 95%.
Preferably, the material constituting the porous film-like carbon layer specifically includes: carbon fiber, carbon nano tube, single-layer graphene, multi-layer graphene, graphene oxide and redox graphene, natural graphite, mesocarbon microbeads, graphite fiber, petroleum coke, needle coke, organic polymer pyrolytic carbon, resin carbon and carbon black.
Preferably, the lithiophilization treatment specifically includes:
cleaning and drying the porous membrane-shaped carbon layer, and then performing infiltration treatment in lithiophilic treatment liquid; the lithiophilization treatment liquid comprises: a solution or colloid containing any one or more of trimethylaluminum, trialkylaluminum, trihydrocarbylaluminum, ethylaluminum, butylaluminum, aluminum acetate, aluminum formate, aluminum oxalate, aluminum propionate, dialkylaluminum chloride, red aluminum, aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum silicate, aluminum sulfide, alum, zinc acetate, zinc stearate, diethylzinc, organozinc halide compounds, dihydrocarbylzinc compounds, lithium zincate, magnesium zincate, diphenylzinc, organozincate, zinc chloride, silver nitrate, silane powder, silane paste, silane mixture, silane emulsion, ethyl silicate, silica sol, methyl silicate, siloxane, and silazane;
and drying the porous membranous carbon layer subjected to the soaking treatment in a vacuum environment and/or sintering the porous membranous carbon layer in an inert atmosphere.
Further preferably, the sintering temperature is 600-1600 ℃ and the time is 2-24 hours;
the drying temperature is 45-300 ℃, and the drying time is 1-24 hours.
Preferably, the step of compounding the lithium metal with the lithiophilized porous film-like carbon layer to obtain the composite lithium metal negative electrode specifically includes:
rolling the metal lithium thin film layer containing the metal lithium and the porous film-shaped carbon layer subjected to lithiation affinity treatment in an inert protective environment to obtain a composite metal lithium cathode; the rolling comprises hot and/or cold pressing; the purity of the metal lithium is not lower than 95%, and the metal lithium film layer is of a structure that the two sides of the metal lithium are sandwiched with lithium-phobic films.
Further preferably, the temperature of the hot pressing is in the range of 50 ℃ to 190 ℃; the inert protective environment is an inert atmosphere or a dry environment;
when the rolling includes hot pressing, after the hot pressing, the method further includes: and (3) preserving the heat of the porous membranous carbon layer film subjected to the hot pressing for 1min to 24 hours at the temperature of 40 ℃ to 200 ℃ in a vacuum oven or an inert atmosphere furnace.
Preferably, after the compounding of the metallic lithium with the lithiophilized porous film-like carbon layer, the method further includes:
storing the composite metal lithium negative electrode in a set atmosphere for more than 20 min; the set atmosphere is any single gas or mixed gas of oxygen, carbon dioxide and nitrogen.
In a second aspect, an embodiment of the present invention provides a composite lithium metal negative electrode prepared by the preparation method in the first aspect, where the composite lithium metal negative electrode includes a lithium-philic carbon skeleton composed of metal lithium and a porous film-like carbon layer after lithiation-philic treatment, and the metal lithium precipitate is attached to the carbon skeleton to form a network channel for lithium ion interconnection during charging and discharging.
In a third aspect, embodiments of the present invention provide a lithium battery including the lithium composite anode described in the second aspect.
The invention provides a preparation method of a composite lithium metal cathode material which is low in price, simple and convenient to prepare and capable of being produced in a large scale. The composite lithium metal cathode obtained by the preparation method can effectively relieve the huge volume change of the lithium metal cathode, solve the problems of the prior art such as low safety, low cycle and low rate characteristics, and simultaneously has a certain inhibition effect on the growth of lithium metal dendrites.
Because the prepared composite metal lithium cathode does not use a cathode current collector, the content of cathode metal lithium is effectively improved, the volume change of the metal lithium cathode in the charging and discharging process can be greatly relieved due to the existence of the carbon skeleton, the mass/volume energy density of the lithium battery can be improved, the cycle performance and the safety performance of the battery are improved, and meanwhile, the electrode has a high specific surface area and the rate capability of the battery can be improved.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
Fig. 1 is a flowchart of a method for manufacturing a lithium composite anode according to an embodiment of the present invention;
fig. 2 is a graph showing charge and discharge performance of the monolithic pouch battery with the composite lithium metal negative electrode provided in example 7 of the present invention at 1 st, 2 nd, and 10 th weeks.
Detailed Description
The invention is further illustrated by the following figures and specific examples, but it should be understood that these examples are for the purpose of illustration only and are not to be construed as in any way limiting the present invention, i.e., as in no way limiting its scope.
The embodiment of the invention provides a composite metal lithium cathode and a preparation method thereof.
The invention provides a composite metal lithium negative electrode, comprising: the lithium-philic carbon framework is formed by metal lithium and the porous membrane-shaped carbon layer after lithiation-philic treatment, and the metal lithium precipitate is attached to the carbon framework to form a network channel for interconnecting and communicating lithium ions in the charging and discharging process.
The preparation method is shown as the preparation method flow in figure 1, and mainly comprises the following steps:
the porous film-like carbon layer of the present invention is composed of a graphite-like carbon material, an amorphous carbon-like material and/or a graphene-like carbon material, and has a thickness of 20 to 200 μm and a porosity of 20 to 95%. Can be prepared by physical method, chemical method or electrochemical method.
Specific materials of the porous film-like carbon layer include, but are not limited to: fibrous carbon such as carbon fiber and carbon nanotube, graphene-like carbon such as single-layer double-layer or multilayer graphene, graphene oxide and redox graphene, natural graphite, artificial graphite such as mesocarbon microbeads and graphite fiber, easily graphitizable soft carbon such as petroleum coke and needle coke, hard carbon such as organic polymer pyrolytic carbon, resin carbon and carbon black, which are not easily graphitizable; wherein the porous film-like carbon layer may be composed of one or more carbon materials described above in a composite manner.
specifically, the process of lithiophilic treatment comprises the following steps:
cleaning and drying the porous membrane-shaped carbon layer, and then performing infiltration treatment in lithiophilic treatment liquid; specific modes include but are not limited to single-point infiltration diffusion, multi-point infiltration diffusion and complete infiltration fusion.
The lithiophilization treatment liquid comprises: a solution or colloid containing any one or more of trimethylaluminum, trialkylaluminum, trihydrocarbylaluminum, ethylaluminum, butylaluminum, aluminum acetate, aluminum formate, aluminum oxalate, aluminum propionate, dialkylaluminum chloride, red aluminum, aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum silicate, aluminum sulfide, alum, zinc acetate, zinc stearate, diethylzinc, organozinc halide compounds, dihydrocarbylzinc compounds, lithium zincate, magnesium zincate, diphenylzinc, organozincate, zinc chloride, silver nitrate, silane powder, silane paste, silane mixture, silane emulsion, ethyl silicate, silica sol, methylsilicate, siloxane, silazane and the like;
and drying the porous membranous carbon layer subjected to the soaking treatment in a vacuum environment and/or sintering the porous membranous carbon layer in an inert atmosphere.
Wherein. The sintering temperature is 600-1600 ℃ and the sintering time is 2-24 hours; the drying temperature is 45-300 ℃ and the drying time is 1-24 hours.
And step 130, compounding the lithium metal with the porous film-shaped carbon layer subjected to lithiation affinity treatment to obtain the composite lithium metal cathode.
Specifically, the compounding is to roll the metal lithium thin film layer and the porous film-shaped carbon layer after the lithiophilization treatment in an inert protective environment to obtain a composite metal lithium cathode; the purity of the used metal lithium is not lower than 95%. The thickness of the metal lithium is 3-200 microns, and the metal lithium film layer is in a structure that the two sides of the metal lithium are sandwiched with lithium-phobic films. The lithium-repellent film may be a film made of lithium comb materials such as an aluminum plastic film, a polyimide film (PI) film, a Polyethylene (PE) film, or a polypropylene film (PP). Wherein rolling comprises hot and/or cold pressing;
when the technological process simultaneously comprises hot pressing and cold pressing, firstly, the metal lithium thin film layer and the porous film-shaped carbon layer are rolled by a hot rolling machine in an inert atmosphere or a drying room, and the hot pressing temperature range is 50-190 ℃; after positive and negative roll pressing for specified times, the porous membranous carbon layer film after hot pressing is kept warm for 1min to 24 hours in a vacuum oven or an inert atmosphere furnace at the temperature of 40 ℃ to 200 ℃. Placing the film after heat preservation in an inert atmosphere or a drying room for cold pressing, wherein the distance between cold pressing rollers is smaller than the thickness of the film after heat preservation, and then placing the film after cold pressing in a set atmosphere for storage for more than 20 min; wherein, the set atmosphere is any single gas or mixed gas of oxygen, carbon dioxide and nitrogen.
When the rolling only comprises hot pressing, after the hot pressing, the porous membranous carbon layer film after the hot pressing is kept at the temperature of 40-200 ℃ for 1-24 hours in a vacuum oven or an inert atmosphere furnace, and then the film is stored for more than 20 minutes in a set atmosphere.
When the rolling only comprises cold pressing, after the cold pressing, the film is also stored in a set atmosphere for more than 20 min.
And cutting the rolled material to form the size of the assembled battery, thus obtaining the composite metal lithium cathode.
In order to better understand the technical solutions provided by the present invention, the following description respectively describes specific processes for preparing a composite lithium metal negative electrode by applying the method provided by the above embodiments of the present invention, and a method for applying the same to a lithium battery and battery characteristics by using a plurality of specific examples.
Example 1
And repeatedly washing the film-shaped porous fiber carbon film with the porosity of 70% and the thickness of 80 microns by deionized water, alcohol and acetone for three times respectively, and drying in a vacuum drying oven to obtain the clean porous film carbon. Preparing 3mol/L zinc acetate aqueous solution by using deionized water, soaking clean porous film carbon into the 3mol/L zinc acetate aqueous solution, stirring for 1 hour, taking out the porous film carbon fully soaked with the zinc acetate aqueous solution, placing the porous film carbon in a room-temperature drying room for drying for 12 hours, and then placing the porous film carbon in a vacuum drying oven for drying for 6 hours at 120 ℃. And (3) placing the dried porous carbon film in a muffle furnace, sintering for 12 hours at 800 ℃ under an inert atmosphere, naturally cooling, and taking out.
And (3) rolling the dried porous carbon film and a 50-micron lithium metal film with 99% purity sandwiched between two surfaces in an inert atmosphere by a hot roller press, wherein the total thickness of the rolled film with more rolled thickness is low, and the temperature of a roller of the hot roller press is 80 ℃. And (4) after the positive and negative roll pressing is carried out for three times, taking out the rolled lithium-carbon composite film, and keeping the temperature in a vacuum oven at 150 ℃ for 2 hours. And (3) cold-pressing the lithium-carbon composite film subjected to heat preservation in an inert atmosphere, wherein the distance between cold-pressing rollers is smaller than that of the lithium-carbon composite film subjected to heat preservation, storing the lithium-carbon composite film subjected to cold pressing in a nitrogen atmosphere for 3 hours, and cutting the lithium-carbon composite film into the size capable of assembling a battery, so that the composite metal lithium cathode is obtained.
And (3) sandwiching a diaphragm between the cut composite metal lithium cathode and the single lithium cobaltate anode, and injecting electrolyte to assemble the single soft package battery with the composite metal lithium cathode.
Example 2
And repeatedly washing the film-shaped porous fiber carbon film with the porosity of 70% and the thickness of 160 microns by deionized water, alcohol and acetone for three times respectively, and drying in a vacuum drying oven to obtain the clean porous film carbon. Preparing 2mol/L zinc acetate aqueous solution by using deionized water, soaking clean porous film carbon into the prepared zinc acetate aqueous solution, stirring for 2 hours, taking out the porous film carbon fully soaked with the zinc acetate aqueous solution, placing the porous film carbon in a room-temperature drying room for drying for 12 hours, and then placing the porous film carbon in a vacuum drying oven for drying for 6 hours at 150 ℃. And (3) placing the dried porous carbon film in a muffle furnace under inert atmosphere at 800 ℃ for sintering for 12 hours, and taking out after naturally cooling.
And (3) rolling the dried porous carbon film and a 100-micron lithium metal film with 99% purity sandwiched between two surfaces in a drying room by a hot roller press, wherein the total thickness of the rolled film with more rolled thickness is low, and the temperature of a roller of the hot roller press is 80 ℃. And (4) after the positive and negative roll pressing is carried out for three times, taking out the rolled lithium-carbon composite film, and keeping the temperature of the lithium-carbon composite film in an inert atmosphere furnace at 150 ℃ for 2 hours. And (3) cold-pressing the heat-insulated lithium-carbon composite film in a drying room, wherein the distance between cold pressing rollers is smaller than that of the heat-insulated lithium-carbon composite film, storing the cold-pressed lithium-carbon composite film in a nitrogen atmosphere for 3 hours, and cutting the cold-pressed lithium-carbon composite film into the size capable of assembling a battery, thereby obtaining the composite metal lithium cathode.
And (3) sandwiching a diaphragm between the cut composite metal lithium cathode and the double-sided lithium cobaltate anode, and filling electrolyte into the diaphragm to form the cylindrical battery with the composite metal lithium cathode.
Example 3
And repeatedly washing the film-shaped porous fiber carbon film with the porosity of 80% and the thickness of 80 microns by deionized water, alcohol and acetone for three times respectively, and drying in a vacuum drying oven to obtain the clean porous film carbon. Preparing a 3mol/L trimethylaluminum aqueous solution by using deionized water, soaking clean porous film carbon into the 3mol/L trimethylaluminum aqueous solution, stirring for 3 hours, taking out the porous film carbon fully soaked with the trimethylaluminum aqueous solution, drying in the room temperature drying room for 12 hours, and then drying in a vacuum drying oven for 8 hours at 110 ℃. And (3) placing the dried porous carbon film in a muffle furnace, sintering for 8 hours at 1000 ℃ in an inert atmosphere, and naturally cooling and taking out.
And (3) rolling the dried porous carbon film and a 60-micron lithium metal film with 99% purity sandwiched between two surfaces in an inert atmosphere by a hot roller press, wherein the total thickness of the rolled film with more rolled thickness is low, and the temperature of a roller of the hot roller press is 80 ℃. And (4) after the positive and negative roll pressing is carried out for three times, taking out the rolled lithium-carbon composite film, and keeping the temperature of the lithium-carbon composite film in an inert atmosphere furnace at 160 ℃ for 3 hours. And (3) cold-pressing the heat-insulated lithium-carbon composite film in a drying room, wherein the distance between cold pressing rollers is smaller than that of the heat-insulated lithium-carbon composite film, storing the cold-pressed lithium-carbon composite film in a nitrogen atmosphere for 2 hours, and cutting the lithium-carbon composite film into the size capable of assembling a battery to obtain the composite metal lithium cathode.
And (3) sandwiching a diaphragm between the cut composite metal lithium cathode and the single iron disulfide anode, and injecting electrolyte to prepare the single soft package battery with the composite metal lithium cathode.
Example 4
And repeatedly washing the film-shaped porous fiber carbon film with the porosity of 70% and the thickness of 180 microns by deionized water, alcohol and acetone for three times respectively, and drying in a vacuum drying oven to obtain the clean porous film carbon. Preparing a 3mol/L trimethylaluminum aqueous solution by using deionized water, soaking clean porous film carbon into a 2mol/L trimethylaluminum aqueous solution, stirring for 2 hours, taking out the porous film carbon fully soaked with the trimethylaluminum aqueous solution, drying in a room-temperature drying room for 12 hours, and then drying in a vacuum drying oven for 8 hours at 180 ℃. And (3) placing the dried porous carbon film in a muffle furnace under inert atmosphere at 900 ℃ for sintering for 8 hours, and taking out after naturally cooling.
And (3) rolling the dried porous carbon film and a 120-micron lithium metal film with 99% purity sandwiched between two surfaces in a drying room by a hot roller press, wherein the total thickness of the rolled film with more rolled thickness is low, and the temperature of a roller of the hot roller press is 80 ℃. And (3) after the positive and negative roll pressing is carried out for three times, taking out the rolled lithium-carbon composite film, and keeping the temperature of the lithium-carbon composite film for 3 hours at 160 ℃ in a vacuum oven or an inert atmosphere furnace. And (3) cold-pressing the lithium-carbon composite film subjected to heat preservation in an inert atmosphere or a drying room, wherein the distance between cold pressing rollers is smaller than that of the lithium-carbon composite film subjected to heat preservation, storing the lithium-carbon composite film subjected to cold pressing in a nitrogen atmosphere for 2 hours, and cutting the lithium-carbon composite film into the size capable of assembling the battery.
And (3) sandwiching a diaphragm between the cut composite metal lithium negative electrode and the double-sided iron disulfide positive electrode, and injecting electrolyte to prepare the multilayer soft package battery with the composite metal lithium negative electrode.
Example 5
And repeatedly washing the film-shaped porous fiber carbon film with the porosity of 70% and the thickness of 80 microns by deionized water, alcohol and acetone for three times respectively, and drying in a vacuum drying oven to obtain the clean porous film carbon. Soaking clean porous film carbon in silica sol, stirring for 5 hr, taking out the porous film carbon soaked with silica sol, drying at room temperature for 24 hr, and drying at 250 deg.c in a vacuum drying oven for 6 hr.
And (3) rolling the dried porous carbon film and the 60-micron lithium metal film with the purity of 99 percent sandwiched between two surfaces in a drying room by a hot roller press, wherein the total thickness of the rolled film with more rolled thickness is low, and the temperature of a roller of the hot roller press is 100 ℃. And (4) after the positive and negative roll pressing is carried out for three times, taking out the rolled lithium-carbon composite film, and keeping the temperature in a vacuum oven at 160 ℃ for 1 hour. And (3) cold-pressing the heat-insulated lithium-carbon composite film in a drying room, wherein the distance between cold pressing rollers is smaller than that of the heat-insulated lithium-carbon composite film, storing the cold-pressed lithium-carbon composite film in a mixed atmosphere of oxygen, carbon dioxide and nitrogen for 3 hours, and cutting the lithium-carbon composite film into the size capable of assembling a battery to obtain the composite metal lithium cathode.
And sandwiching the cut composite metal lithium cathode into a diaphragm relative to the single nickel manganese aluminum lithium anode, and injecting electrolyte to assemble the single soft package battery with the composite metal lithium cathode.
Example 6
And repeatedly washing the film-shaped porous fiber carbon film with the porosity of 70% and the thickness of 160 microns by deionized water, alcohol and acetone for three times respectively, and drying in a vacuum drying oven to obtain the clean porous film carbon. Soaking clean porous film carbon in silica sol, stirring for 6 hr, taking out the porous film carbon soaked with silica sol, drying in room temperature for 24 hr, stoving in vacuum drying oven at 100 deg.c for 12 hr, and taking out.
And (3) rolling the dried porous carbon film and the 120-micron lithium metal film with the purity of 99 percent sandwiched between two surfaces in an inert atmosphere or a drying room by using a hot roller press, wherein the total thickness of the rolled film with more rolled thickness is low, and the temperature of a roller of the hot roller press is 90 ℃. And (4) after the positive and negative roll pressing is carried out for three times, taking out the rolled lithium-carbon composite film, and keeping the temperature of the lithium-carbon composite film for 1 hour at 160 ℃ in an inert atmosphere furnace. And (3) cold-pressing the heat-insulated lithium-carbon composite film in a drying room, wherein the distance between cold pressing rollers is smaller than that of the heat-insulated lithium-carbon composite film, storing the cold-pressed lithium-carbon composite film in the drying room for 3 hours, and cutting the lithium-carbon composite film into the size capable of assembling a battery, thereby obtaining the composite metal lithium cathode.
And (3) sandwiching a diaphragm between the cut composite metal lithium negative electrode and the double-sided sulfur-carbon positive electrode, and injecting electrolyte to prepare the multilayer soft package battery with the composite metal lithium negative electrode.
Example 7
And repeatedly washing the film-shaped porous fiber carbon film with the porosity of 70% and the thickness of 100 microns by deionized water, alcohol and acetone for three times respectively, and drying in a vacuum drying oven to obtain the clean porous film carbon. Soaking clean porous film carbon in silica sol, stirring for 6 hr, taking out the porous film carbon soaked with silica sol, drying in room temperature for 24 hr, stoving in vacuum drying oven at 120 deg.c for 12 hr, and taking out.
And (3) rolling the dried porous carbon film and a 70-micron lithium metal film with 99% purity sandwiched between two surfaces in an inert atmosphere by a hot roller press, wherein the total thickness of the rolled film with more rolled thickness is low, and the temperature of a roller of the hot roller press is 80 ℃. And (3) after the positive and negative roll pressing is carried out for three times, taking out the rolled lithium-carbon composite film, and keeping the temperature of the lithium-carbon composite film for 1 hour at 120 ℃ in a vacuum oven or an inert atmosphere furnace. And (3) cold-pressing the lithium-carbon composite film subjected to heat preservation in an inert atmosphere, wherein the distance between cold-pressing rollers is smaller than that of the lithium-carbon composite film subjected to heat preservation, storing the lithium-carbon composite film subjected to cold pressing in a drying room for 12 hours, and cutting the lithium-carbon composite film into the size capable of assembling the battery.
And (3) sandwiching a diaphragm between the cut composite metal lithium negative electrode and the single-side iron disulfide positive electrode, injecting electrolyte, and assembling the single-piece soft package battery with the composite metal lithium negative electrode, wherein the battery performance is shown in figure 2.
Example 8
And repeatedly washing the film-shaped porous fiber carbon film with the porosity of 70% and the thickness of 180 microns by deionized water, alcohol and acetone for three times respectively, and drying in a vacuum drying oven to obtain the clean porous film carbon. Preparing a 3mol/L trimethylaluminum aqueous solution by using deionized water, soaking clean porous film carbon into a 2mol/L trimethylaluminum aqueous solution, stirring for 2 hours, taking out the porous film carbon fully soaked with the trimethylaluminum aqueous solution, placing the porous film carbon in a room-temperature drying room for drying for 12 hours, and then placing the porous film carbon in a vacuum drying oven for drying for 8 hours at 160 ℃. And (3) placing the dried porous carbon film in a muffle furnace under inert atmosphere at 900 ℃ for sintering for 8 hours, and taking out after naturally cooling.
And (3) rolling the dried porous carbon film and the 120-micron lithium metal film with 99% purity sandwiched between two surfaces in an inert atmosphere or a drying room by using a hot roller press, wherein the total thickness of the rolled film with more rolled thickness is low, and the temperature of a roller of the hot roller press is 80 ℃. And (4) after the positive and negative roll pressing is carried out for three times, taking out the rolled lithium-carbon composite film, and keeping the temperature of the lithium-carbon composite film in an inert atmosphere furnace at 160 ℃ for 3 hours. And (3) cold-pressing the lithium-carbon composite film subjected to heat preservation in an inert atmosphere, wherein the distance between cold-pressing rollers is smaller than that of the lithium-carbon composite film subjected to heat preservation, storing the lithium-carbon composite film subjected to cold pressing in a nitrogen atmosphere for 2 hours, and cutting the lithium-carbon composite film into the size capable of assembling the battery.
And (3) sandwiching a diaphragm between the cut composite metal lithium negative electrode and the double-sided iron disulfide positive electrode, and injecting electrolyte to prepare the multilayer soft package battery with the composite metal lithium negative electrode.
Example 9
And repeatedly washing the film-shaped porous fiber carbon film with the porosity of 70% and the thickness of 180 microns by deionized water, alcohol and acetone for three times respectively, and drying in a vacuum drying oven to obtain the clean porous film carbon. Preparing 1mol/L alum aqueous solution by using deionized water, soaking clean porous film carbon in 1mol/L alum aqueous solution, stirring for 2 hours, taking out the porous film carbon fully soaked with the alum solution, placing the porous film carbon in a room temperature drying room for drying for 12 hours, and then placing the porous film carbon in a vacuum drying oven for drying for 8 hours at 130 ℃. And then placing the dried porous carbon film in a muffle furnace under inert atmosphere at 1000 ℃ for sintering for 6 hours, and taking out after naturally cooling.
And (3) rolling the dried porous carbon film and the 120-micron lithium metal film with 99% purity sandwiched between two surfaces in a drying room by a hot roller press, wherein the total thickness of the rolled film with more rolled thickness is low, and the temperature of a roller of the hot roller press is 80 ℃. And (4) after the positive and negative roll pressing is carried out for three times, taking out the rolled lithium-carbon composite film, and preserving the heat for 3 hours in a vacuum oven at 150 ℃. And (3) cold pressing the heat-insulated lithium-carbon composite film in a drying room, wherein the distance between cold pressing rollers is smaller than that of the heat-insulated lithium-carbon composite film, storing the cold-pressed lithium-carbon composite film in a nitrogen atmosphere for 2 hours, and cutting the lithium-carbon composite film into the size capable of assembling the battery.
And (3) sandwiching a diaphragm between the cut composite metal lithium negative electrode and the double-sided lithium manganate positive electrode, and filling electrolyte into the diaphragm to prepare the multilayer soft package battery with the composite metal lithium negative electrode.
Example 10
And repeatedly washing the film-shaped porous fiber carbon film with the porosity of 70% and the thickness of 180 microns by deionized water, alcohol and acetone for three times respectively, and drying in a vacuum drying oven to obtain the clean porous film carbon. Preparing 3mol/L of alum aqueous solution by using deionized water, soaking clean porous film carbon into the 3mol/L of alum aqueous solution, stirring for 2 hours, taking out the porous film carbon fully soaked with the alum solution, placing the porous film carbon in a room-temperature drying room for drying for 12 hours, and then placing the porous film carbon in a vacuum drying oven for drying for 8 hours at 150 ℃. And then placing the dried porous carbon film in a high-temperature furnace to sinter for 8 hours at 800 ℃ under the inert atmosphere, and taking out after naturally cooling.
And (3) rolling the dried porous carbon film and the 120-micron lithium metal film with the purity of 98 percent sandwiched between the two surfaces in an inert atmosphere or a drying room by using a hot roller press, wherein the total thickness of the rolled film with more rolled thickness is low, and the temperature of a roller of the hot roller press is 80 ℃. And (4) after the positive and negative roll pressing is carried out for three times, taking out the rolled lithium-carbon composite film, and preserving the heat for 3 hours at 150 ℃ in a vacuum oven or an inert atmosphere furnace. And (3) cold-pressing the lithium-carbon composite film subjected to heat preservation in an inert atmosphere or a drying room, wherein the distance between cold pressing rollers is smaller than that of the lithium-carbon composite film subjected to heat preservation, storing the lithium-carbon composite film subjected to cold pressing in a nitrogen atmosphere for 2 hours, and cutting the lithium-carbon composite film into the size capable of assembling the battery.
And (3) sandwiching a diaphragm between the cut composite metal lithium negative electrode and the double-sided lithium manganate positive electrode, and filling electrolyte into the composite metal lithium negative electrode to form the cylindrical battery with the composite metal lithium negative electrode.
In the above embodiments, a large-area uniform composite metal lithium negative electrode is successfully prepared by first constructing a thin-film porous carbon layer, then forming a lithium-philic layer inside or on the surface of the porous carbon layer, and then fusing metal lithium and the porous thin-film carbon layer by melting, rolling, heat preservation and other methods to form the composite metal lithium carbon negative electrode. The composite metal lithium prepared by the method has controllable negative electrode surface capacity, good cyclicity and small battery polarization, and can be used in a liquid or solid battery system.
The invention provides a preparation method of a composite lithium metal cathode material which is low in price, simple and convenient to prepare and capable of being produced in a large scale. The composite lithium metal cathode obtained by the preparation method can effectively relieve the huge volume change of the lithium metal cathode, solve the problems of the prior art such as low safety, low cycle and low rate characteristics, and simultaneously has a certain inhibition effect on the growth of lithium metal dendrites.
Because the prepared composite metal lithium cathode does not use a cathode current collector, the content of cathode metal lithium is effectively improved, the volume change of the metal lithium cathode in the charging and discharging process can be greatly relieved due to the existence of the carbon skeleton, the mass/volume energy density of the lithium battery can be improved, the cycle performance and the safety performance of the battery are improved, and meanwhile, the electrode has a high specific surface area and the rate capability of the battery can be improved.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for preparing a composite lithium metal anode, the method comprising:
preparing a porous film-shaped carbon layer;
subjecting the porous film-like carbon layer to lithiation-philic treatment;
compounding the metal lithium with the porous film-shaped carbon layer subjected to lithiation-philic treatment to obtain a composite metal lithium cathode;
in the composite metal lithium cathode, the porous film-shaped carbon layer subjected to lithiation affinity treatment forms a lithium affinity carbon framework, and metal lithium precipitates are attached to the carbon framework to form a network channel for interconnecting and communicating lithium ions in the charging and discharging process.
2. The method for producing a composite metal lithium anode according to claim 1, wherein the porous film-like carbon layer is composed of a graphite-like carbon material, an amorphous-like carbon material, and/or a graphene-like carbon material;
the porous film-like carbon layer has a thickness of 20 to 200 μm and a porosity of 20 to 95%.
3. The method of manufacturing a composite lithium metal anode according to claim 1, wherein a material constituting the porous film-like carbon layer specifically includes: carbon fiber, carbon nano tube, single-layer graphene, multi-layer graphene, graphene oxide and redox graphene, natural graphite, mesocarbon microbeads, graphite fiber, petroleum coke, needle coke, organic polymer pyrolytic carbon, resin carbon and carbon black.
4. The method for producing a composite metal lithium negative electrode according to claim 1, characterized in that the lithiophilization treatment specifically includes:
cleaning and drying the porous membrane-shaped carbon layer, and then performing infiltration treatment in lithiophilic treatment liquid; the lithiophilization treatment liquid comprises: a solution or colloid containing any one or more of trimethylaluminum, trialkylaluminum, trihydrocarbylaluminum, ethylaluminum, butylaluminum, aluminum acetate, aluminum formate, aluminum oxalate, aluminum propionate, dialkylaluminum chloride, red aluminum, aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum silicate, aluminum sulfide, alum, zinc acetate, zinc stearate, diethylzinc, organozinc halide compounds, dihydrocarbylzinc compounds, lithium zincate, magnesium zincate, diphenylzinc, organozincate, zinc chloride, silver nitrate, silane powder, silane paste, silane mixture, silane emulsion, ethyl silicate, silica sol, methyl silicate, siloxane, and silazane;
and drying the porous membranous carbon layer subjected to the soaking treatment in a vacuum environment and/or sintering the porous membranous carbon layer in an inert atmosphere.
5. The method of producing a composite lithium metal anode according to claim 4,
the sintering temperature is 600-1600 ℃ and the sintering time is 2-24 hours;
the drying temperature is 45-300 ℃, and the drying time is 1-24 hours.
6. The method for preparing a composite metal lithium negative electrode according to claim 1, wherein the step of compounding the metal lithium with the lithiophilized porous film-like carbon layer to obtain the composite metal lithium negative electrode specifically comprises:
rolling the metal lithium thin film layer containing the metal lithium and the porous film-shaped carbon layer subjected to lithiation affinity treatment in an inert protective environment to obtain a composite metal lithium cathode; the rolling comprises hot and/or cold pressing; the purity of the metal lithium is not lower than 95%, and the metal lithium film layer is of a structure that the two sides of the metal lithium are sandwiched with lithium-phobic films.
7. The method of preparing a lithium composite metal anode according to claim 6, wherein the temperature of the hot pressing is in the range of 50 ℃ to 190 ℃; the inert protective environment is an inert atmosphere or a dry environment;
when the rolling includes hot pressing, after the hot pressing, the method further includes: and (3) preserving the heat of the porous membranous carbon layer film subjected to the hot pressing for 1min to 24 hours at the temperature of 40 ℃ to 200 ℃ in a vacuum oven or an inert atmosphere furnace.
8. The method for producing a composite metal lithium anode according to claim 1, characterized in that, after the compounding of metal lithium with the lithiophilized porous film-like carbon layer, the method further comprises:
storing the composite metal lithium negative electrode in a set atmosphere for more than 20 min; the set atmosphere is any single gas or mixed gas of oxygen, carbon dioxide and nitrogen.
9. The composite lithium metal negative electrode prepared by the preparation method of any one of claims 1 to 8, wherein the composite lithium metal negative electrode comprises a lithium-philic carbon skeleton consisting of lithium metal and a porous film-shaped carbon layer subjected to lithiation-philic treatment, and lithium metal precipitates are attached to the carbon skeleton to form network channels for interconnecting and communicating lithium ions in the charging and discharging processes.
10. A lithium battery comprising the lithium composite metal negative electrode according to claim 9.
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