CN111725515A - Stable lithium powder and preparation method and application thereof - Google Patents
Stable lithium powder and preparation method and application thereof Download PDFInfo
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention discloses stable lithium powder and a preparation method and application thereof. Wherein the method of preparing the stabilized lithium powder comprises: mixing and reacting fluorine-containing acid salt, lithium powder and an organic solvent to form a lithium fluoride passivation layer on the surface of the lithium powder so as to obtain stable lithium powder, wherein the mass ratio of the lithium fluoride passivation layer to the lithium powder in the stable lithium powder is (0.5-1.8): 1. The method for preparing the stable lithium powder is simple in process, and the prepared stable lithium powder has high stability and long storage life, is convenient for safe transportation, storage and use of the lithium powder, and can be widely used as a lithium supplement additive of a lithium battery electrode material.
Description
Technical Field
The invention belongs to the field of lithium batteries, and particularly relates to stable lithium powder and a preparation method and application thereof.
Background
Lithium ion batteries are widely used because of their advantages of high operating voltage, large specific energy, small volume, light weight, long cycle life, low self-discharge, no memory effect, no pollution, etc. In recent years, with the rapid development of new energy automobiles, smart grids and distributed energy storage, higher requirements are put forward on the energy density of lithium ion batteries. The cathode material of the traditional lithium ion battery is graphite and carbon material, and the anode material comprises lithium cobaltate, lithium manganate, lithium iron phosphate and other materials. At present, most commercial lithium ion batteries adopt a carbonaceous negative electrode, generally adopt a graphite-based material, and have low lithium intercalation capacity (372 mAh/g). During charge and discharge, consumption of lithium ions coupled with decomposition of the electrolyte forms a passive protective layer (commonly referred to as SEI (solid electrolyte interface)) on the surface of the graphite negative electrode. In theory, the SEI film only transmits lithium ions, but blocks the transmission of electrons, thereby preventing further degradation of the electrolyte and enabling stable cycling of a lithium ion battery with a carbonaceous negative electrode. The SEI film is mainly formed during the first several charging processes, especially during the first charging process, resulting in rapid reduction of the battery capacity. As the battery charge and discharge progresses, the graphite negative electrode material undergoes a volume change of about 10% due to the intercalation and deintercalation of lithium ions. The SEI film may be broken due to a change in volume, causing the lithiated graphite to contact and react with the electrolyte, thereby consuming the electrolyte and lithium ions. This results in the continuous generation and thickening of the SEI film, resulting in the contact and reaction of lithiated graphite with the electrolyte, thereby consuming the electrolyte and lithium ions, and the available capacity and internal resistance of the battery are continuously decreased and increased.
In recent years, silicon-based negative electrode batteries have been developed rapidly. The silicon-based negative electrode material has the advantages of high specific capacity (up to 4200mAh/g, which is far higher than 372mAh/g of graphite), low cost, low embedded potential and the like, and is considered to be one of the most promising negative electrode materials of next-generation high-specific-energy lithium ion batteries. Since the potential is outside the electrolyte stability window, an SEI film is also formed, resulting in low initial cycle coulombic efficiency. The increasing thickness of the SEI film also results in irreversible loss of lithium ions, permanently consuming a large amount of lithium from the positive electrode, resulting in a low first cycle coulombic efficiency (ICE), and reducing the capacity and energy density of the lithium ion battery. In addition, during the lithiation process, the silicon can expand greatly by 300-400%, which may cause the subsequent SEI film generation and active material pulverization, resulting in the active material peeling off on the current collector. Further, since the conductivity is poor and the capacity cannot be sufficiently utilized, the power density is also poor. Therefore, many researchers have been devoted to the study of silicon/carbon composite anode materials to improve the service life and rate performance thereof.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, it is an object of the present invention to provide stabilized lithium powders, methods for their preparation and their use. The method for preparing the stable lithium powder is simple in process, and the prepared stable lithium powder has high stability and long storage life, is convenient for safe transportation, storage and use of the lithium powder, and can be widely used as a lithium supplement additive of a lithium battery electrode material.
The invention is mainly based on the following problems:
currently, lithium can be supplemented to an electrode material through prelithiation to offset irreversible lithium loss caused by the formation of an SEI film, so as to improve the total capacity and energy density of a battery. The addition amount of the anode material is increased, the prelithiation additive is used, the electrochemical prelithiation is adopted, the electrode prelithiation is carried out in a contact short circuit mode and the like, the irreversible capacity loss of the first circulation can be compensated to a certain extent, and the economic cost is increased or the complexity of the experimental process is enhanced. Aiming at the problems in the lithium ion battery, the best solution is to add extra active lithium into the negative pole piece, but the use of the negative pole piece for independently forming and supplementing lithium is difficult to operate, and because the activity of lithium is higher, fire disasters can be caused due to excessive active lithium powder, and the potential safety hazard is larger.
To this end, according to a first aspect of the present invention, the present invention proposes a method of preparing a stabilized lithium powder. According to an embodiment of the invention, the method comprises: mixing and reacting fluorine-containing acid salt, lithium powder and an organic solvent to form a lithium fluoride passivation layer on the surface of the lithium powder so as to obtain stable lithium powder, wherein the mass ratio of the lithium fluoride passivation layer to the lithium powder in the stable lithium powder is (0.5-1.8): 1.
According to the method for preparing the stable lithium powder, lithium fluoride which is low in solubility in water and can exist stably is used for coating the surface of the metal lithium powder to generate a continuous and dense passivation protective layer, and compared with the traditional metal lithium powder, the stable lithium powder has higher specific capacity, and the utilization rate of the metal lithium is greatly improved. In addition, the inventor finds that when the mass ratio of the lithium fluoride passivation layer to the lithium powder is too small, the passivation layer is too thin, the coating effect on the lithium powder is poor, the activity of the lithium powder is high, and the lithium powder is easy to react with water and oxygen in the air when exposed to the external environment, so that the lithium powder is rapidly oxidized and even ignited, the stability is poor, and the potential safety hazard is large; and if the mass ratio of the lithium fluoride passivation layer to the lithium powder is too large, the passivation layer is thick, the content of metal lithium in the stable lithium powder added in the pre-lithiation process is low, the dissolution rate of the metal lithium is reduced, the effect of improving the first efficiency of the battery is not obvious, the effect of improving the capacity, the first efficiency and the cycling stability of the battery is poor, and even the inherent performance of the battery is influenced, and the mass ratio of the lithium fluoride passivation layer to the lithium powder is controlled to be (0.5-1.8): 1, the coating layer can be ensured to have proper thickness, the stability of the lithium powder is obviously improved, the stable use of the lithium powder in a low-humidity environment is realized, and meanwhile, the stable lithium powder is used for pre-lithiation to form a lithium supplement layer on the surface of a pole piece in a dry environment in a dry dispersion or wet dispersion mode, so that the first efficiency, the capacity and the cycling stability of the battery can be obviously improved. In conclusion, the method is simple in process, the prepared stable lithium powder has high stability and long storage life, the lithium powder is convenient to safely transport, store and use, and the stable lithium powder can be widely used as a lithium supplement additive of a lithium battery electrode material, and the problem of low first effect of the lithium battery is solved through lithium supplement, so that the comprehensive performances of the first effect, the capacity, the cycle life and the like of the battery are improved.
In addition, the method of preparing the stabilized lithium powder according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, a method of preparing a stabilized lithium powder comprises: (1) mixing and stirring the fluorine-containing acid salt and the organic solvent to obtain a fluorine source solution; (2) mixing the lithium powder with the fluorine source solution under an inert atmosphere and heating and stirring the mixture so as to react the lithium powder with the fluorine source solution; (3) and (3) filtering, cleaning and drying the product obtained in the step (2) so as to obtain the stable lithium powder with the surface provided with the lithium fluoride passivation layer.
In some embodiments of the present invention, in the step (2), the temperature of the heating and stirring is 25 to 120 ℃, the stirring speed is 500 to 2000rpm, and the time is 60 to 720 min.
In some embodiments of the present invention, in the step (3), the filtration is performed by suction filtration using a buchner funnel or natural filtration using a filter screen, and the solvent used for the washing is at least one selected from alkanes, alkenes and aromatic hydrocarbons having a boiling point of less than 150 ℃.
In some embodiments of the present invention, the lithium powder has a particle size of 10 to 100 μm.
In some embodiments of the present invention, the thickness of the passivation layer is 50 to 500 nm.
In some embodiments of the invention, the mass ratio of the fluorine-containing acid salt to the lithium powder is (1-5): 1.
in some embodiments of the present invention, the fluorine-containing acid salt is at least one selected from the group consisting of ammonium bifluoride, sodium bifluoride, and potassium bifluoride.
In some embodiments of the present invention, the organic solvent is at least one selected from the group consisting of dimethyl sulfoxide, acetone, dimethylformamide, dimethylacetamide, 1, 3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide, and propylene carbonate.
According to a second aspect of the invention, a stabilized lithium powder is provided. According to an embodiment of the present invention, the stabilized lithium powder is obtained by the above-described method for preparing a stabilized lithium powder. The stable lithium powder has high stability and long storage life, is convenient for safe transportation, storage and use of the lithium powder, can be widely used as a lithium supplement additive of a lithium battery electrode material, and solves the problem of low initial efficiency of the lithium battery through lithium supplement, thereby improving the capacity, cycle life and other comprehensive properties of the battery.
According to a third aspect of the present invention, a negative electrode sheet is provided. According to an embodiment of the present invention, the process of preparing the negative electrode sheet includes: and carrying out pre-lithiation on the stable lithium powder or the stable lithium powder obtained by the preparation method. When the negative plate is used in a battery, the comprehensive performances of the battery such as the first efficiency, the battery capacity and the cycle life can be obviously improved.
In some embodiments of the present invention, the negative electrode sheet is a silicon-based negative electrode sheet.
According to a fourth aspect of the present invention, a lithium battery is provided. According to an embodiment of the present invention, the lithium battery has the above negative electrode tab. The lithium battery has relatively high first efficiency and good comprehensive performances such as battery capacity, cycle life and the like.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic structural view of a stabilized lithium powder according to one embodiment of the present invention;
FIG. 2 is a schematic flow diagram for preparing stabilized lithium powder according to one embodiment of the present invention;
FIG. 3 is a transmission electron micrograph of a stabilized lithium powder prepared according to example 1 of the present invention;
fig. 4 is a graph showing the change of capacity decay with storage time obtained by sampling the button cell prepared by storing the lithium powders coated with the polymers of examples 1 to 3 in a dry environment (temperature 22 ℃ and humidity < 5%) for different times and performing a capacity test.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
According to a first aspect of the present invention, a method of preparing a stabilized lithium powder is provided. According to an embodiment of the invention, the method comprises: mixing and reacting fluorine-containing acid salt, lithium powder and an organic solvent to form a lithium fluoride passivation layer on the surface of the lithium powder so as to obtain stable lithium powder, wherein the mass ratio of the lithium fluoride passivation layer to the lithium powder in the stable lithium powder is (0.5-1.8): 1, and the structure of the stable lithium powder is shown in figure 1. The method can take a proper amount of metal lithium powder to react in an organic solution containing fluorine acid salt for a period of time in an inert gas atmosphere, so that lithium fluoride is generated on the surfaces of lithium metal particles, and the stabilized metal lithium powder is prepared. The stable lithium powder with the fluorinated surface can be stably stored in the air for a long time, when the stable lithium powder is applied to an electrode material, the pre-lithiation of the lithium ion battery can be realized in a mode of mixing battery slurry or coating the stable lithium powder on the surface of a negative electrode pole piece, and the like, so that the use is convenient, and the process is easy to realize. Therefore, convenience is brought to storage of lithium powder, convenience is brought to the pre-lithiation process of the lithium ion battery cathode material, and the first cycle efficiency and the first capacity of the cathode material can be greatly improved.
The method for preparing the stabilized lithium powder according to the above embodiment of the present invention will be described in detail.
According to the embodiment of the invention, the inventor finds that when the mass ratio of the lithium fluoride passivation layer to the lithium powder is too small, the passivation layer is too thin, the coating effect on the lithium powder is poor, and the lithium powder has high activity, and is easy to react with water and oxygen in the air when being exposed to the external environment, so that the lithium powder is rapidly oxidized and even ignited, the stability is poor, and the potential safety hazard is large; and if the mass ratio of the lithium fluoride passivation layer to the lithium powder is too large, the passivation layer is thick, the content of metal lithium in the stable lithium powder added in the pre-lithiation process is low, the dissolution rate of the metal lithium is reduced, the effect of improving the first efficiency of the battery is not obvious, the effect of improving the capacity, the first efficiency and the cycling stability of the battery is poor, and even the inherent performance of the battery is influenced, when the mass ratio of the lithium fluoride passivation layer to the lithium powder is controlled to be (0.5-1.8), the coating layer can be ensured to have proper thickness, the stability of the lithium powder is obviously improved, the stable use of the lithium powder in a low-humidity environment is realized, and meanwhile, the stable lithium powder is used for pre-lithiation to form a lithium supplement layer on the surface of a pole piece in a dry environment in a dry dispersion or wet dispersion mode, so that the first efficiency, the capacity and the cycling stability. According to an embodiment of the present invention, referring to fig. 2, the method of preparing the stabilized lithium powder may specifically include: (1) mixing and stirring fluorine-containing acid salt and an organic solvent to obtain a fluorine source solution; (2) mixing lithium powder and a fluorine source solution under an inert atmosphere, heating and stirring so as to enable the lithium powder to react with the fluorine source solution; (3) and (3) filtering, cleaning and drying the product obtained in the step (2) so as to obtain the stable lithium powder with the surface provided with the lithium fluoride passivation layer. Therefore, the stable lithium powder with high stability and long storage life can be further obtained, so that the stable lithium powder is more favorable for safe transportation, storage and use of the lithium powder, can be used as a lithium supplement additive of a lithium battery electrode material, and solves the problem of low initial efficiency of the lithium battery through lithium supplement, thereby improving the capacity, cycle life and other comprehensive properties of the battery.
According to still another embodiment of the present invention, in the step (2), the temperature of heating and stirring may be 25 to 120 ℃, for example, 30 ℃, 60 ℃, 90 ℃ or 120 ℃, and the like, the stirring rate may be 500 to 2000rpm, and the time may be 60 to 720min, and the inventors found that the heating temperature, the stirring rate or the reaction time all affect the thickness, uniformity and bonding strength with the lithium powder particles of the lithium fluoride coating layer on the surface of the lithium powder, wherein if the heating temperature is too high, the stirring rate is too fast, and the reaction time is too long, the lithium fluoride coating layer is too thick, the bonding strength with the lithium powder is poor, and the effective lithium capacity is reduced; if the heating temperature is too low, the stirring speed is too low, and the reaction time is too short, the coating layer is incomplete, the stability of the lithium powder is poor, and the dispersibility is reduced. Further, in the step (3), the filtration may be performed by suction filtration using a buchner funnel or natural filtration using a filter screen, and the solvent used for washing may be at least one selected from the group consisting of alkanes, alkenes, and aromatic hydrocarbons having a boiling point of less than 150 ℃, so that it is more advantageous to obtain pure stable lithium powder.
According to another embodiment of the present invention, the particle size of the lithium powder may be 10 to 100 μm, for example, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, or 100 μm, and further, for example, 15 to 25 μm, and the inventors found that the reactivity of the lithium metal particles is very high, and if the particle size of the lithium powder is too small, the specific surface area is too large, more fluorine sources are required to prepare the stable lithium powder, and safety accidents are easily caused; if the particle size of the lithium powder is too large, the stable lithium powder required in the pre-lithiation process cannot be uniformly distributed in a negative electrode material (such as a silicon-oxygen negative electrode), so that excessive lithium supplement is easily caused, the kinetics of lithium metal ion extraction during the pre-lithiation process is poor, and the pre-lithiation effect is influenced. According to the invention, by controlling the lithium powder to be in the range, the safety of the preparation process can be further improved, and the lithium powder with the prepared temperature can achieve a better pre-lithiation effect when being used for pre-lithiation, so that the comprehensive performances of the battery, such as first effect, cycle performance, safety performance and the like, can be obviously improved. Further, the thickness of the passivation layer may be 50 to 500nm, for example, 50nm, 80nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm or 500nm, and the inventors found that if the thickness of the passivation layer is too small, the coating effect on the lithium powder is poor, and safety accidents are also easily caused, and if the thickness of the passivation layer is too large, the dissolution efficiency of the lithium powder is greatly reduced, and the effect of improving the first efficiency of the battery is not obvious. According to the invention, by controlling the lithium powder and the passivation layer to be within the parameter ranges, the stable lithium powder can be further ensured to have high stability and long storage life, and the pre-lithiation effect can be remarkably improved when the stable lithium powder is used as a pre-lithiation additive.
According to another embodiment of the invention, the mass ratio of the fluorine-containing acid salt to the lithium powder is (1-5): 1, by controlling the mass ratio range of the fluorine-containing acid salt to the lithium powder, the passivation layer has a proper thickness, the coating effect on the lithium powder is ensured, and the mass ratio of the passivation layer to the lithium powder is more favorably (0.5-1.8): the stable lithium powder of 1 can obviously improve the stability of the lithium powder, and further can ensure better pre-lithiation effect when the prepared stable lithium powder is used for pre-lithiation, and obviously improve the comprehensive properties of the battery, such as first effect, cycle performance, safety performance and the like.
According to still another embodiment of the present invention, the types of the fluorine-containing acid salt and the organic solvent in the present invention are not particularly limited and can be selected by those skilled in the art according to actual needs. For example, the fluorine-containing acid salt may be at least one selected from the group consisting of ammonium bifluoride, sodium bifluoride and potassium bifluoride, and the organic solvent may be at least one selected from the group consisting of dimethyl sulfoxide, acetone, dimethylformamide, dimethylacetamide, 1, 3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide and propylene carbonate.
In summary, in the method for preparing stable lithium powder according to the above embodiment of the present invention, lithium fluoride having low solubility in water and capable of stably existing is used to coat the surface of the metal lithium powder to generate a continuous and dense passivation protective layer, and the stable lithium powder has a higher specific capacity than the conventional metal lithium powder, thereby greatly improving the utilization rate of the metal lithium. In addition, the inventor finds that when the mass ratio of the lithium fluoride passivation layer to the lithium powder is too small, the passivation layer is too thin, the coating effect on the lithium powder is poor, the activity of the lithium powder is high, and the lithium powder is easy to react with water and oxygen in the air when exposed to the external environment, so that the lithium powder is rapidly oxidized and even ignited, the stability is poor, and the potential safety hazard is large; and if the mass ratio of the lithium fluoride passivation layer to the lithium powder is too large, the passivation layer is thick, the content of metal lithium in the stable lithium powder added in the pre-lithiation process is low, the dissolution rate of the metal lithium is reduced, the effect of improving the first efficiency of the battery is not obvious, the effect of improving the capacity, the first efficiency and the cycling stability of the battery is poor, and even the inherent performance of the battery is influenced, and the mass ratio of the lithium fluoride passivation layer to the lithium powder is controlled to be (0.5-1.8): 1, the coating layer can be ensured to have proper thickness, the stability of the lithium powder is obviously improved, the stable use of the lithium powder in a low-humidity environment is realized, and meanwhile, the stable lithium powder is used for pre-lithiation to form a lithium supplement layer on the surface of a pole piece in a dry environment in a dry dispersion or wet dispersion mode, so that the first efficiency, the capacity and the cycling stability of the battery can be obviously improved. In conclusion, the method is simple in process, the prepared stable lithium powder has high stability and long storage life, the lithium powder is convenient to safely transport, store and use, and the stable lithium powder can be widely used as a lithium supplement additive of a lithium battery electrode material, and the problem of low first effect of the lithium battery is solved through lithium supplement, so that the capacity, the cycle life and other comprehensive properties of the battery are improved.
According to a second aspect of the invention, a stabilized lithium powder is provided. According to an embodiment of the present invention, the stabilized lithium powder is obtained by the above-described method for preparing a stabilized lithium powder. The stable lithium powder has high stability and long storage life, is convenient for safe transportation, storage and use of the lithium powder, can be widely used as a lithium supplement additive of a lithium battery electrode material, and solves the problem of low initial efficiency of the lithium battery through lithium supplement, thereby improving the capacity, cycle life and other comprehensive properties of the battery. It should be noted that the features and effects described for the above method for preparing stabilized lithium powder are also applicable to the stabilized lithium powder, and are not described in detail herein.
According to a third aspect of the present invention, a negative electrode sheet is provided. According to an embodiment of the present invention, the process of preparing the negative electrode sheet includes: and carrying out pre-lithiation on the stable lithium powder or the stable lithium powder obtained by the preparation method. When the negative plate is used in a battery, the comprehensive performances of the battery such as the first efficiency, the battery capacity and the cycle life can be obviously improved.
According to an embodiment of the present invention, during the prelithiation process, the stable lithium powder may be dispersed in an organic solvent, and then the dispersion may be sprayed on the negative electrode sheet, and then the residual organic solvent on the negative electrode sheet is dried, so that lithium may be doped into the electrode material in advance to complete the "lithium supplement". During formation, the stable lithium powder sprayed on the negative electrode can be consumed in the formation of an SEI film, so that lithium ions extracted from the positive electrode are retained to the maximum extent, and the first cycle efficiency and the capacity of the lithium ion battery are improved.
According to another embodiment of the present invention, the negative electrode sheet may be a silicon-based negative electrode sheet, such as a graphite/silica negative electrode sheet, so that the capacity and energy density of the battery may be further improved.
It should be noted that the features and effects described for the above-mentioned lithium stabilizing powder and the method for preparing the lithium stabilizing powder are also applicable to the negative electrode sheet, and are not described in detail herein.
According to a fourth aspect of the present invention, a lithium battery is provided. According to an embodiment of the present invention, the lithium battery has the above negative electrode tab. The lithium battery has relatively high first efficiency and good comprehensive performances such as battery capacity, cycle life and the like. It should be noted that the features and effects described for the above negative electrode plate are also applicable to the lithium battery, and are not described in detail here.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
EXAMPLE 1
Under the atmosphere of argon, 1g of ammonium bifluoride is added into a glass three-neck flask, 100mL of dimethyl sulfoxide solvent is added into the flask, after ammonium bifluoride was sufficiently dissolved by rapid stirring (500rpm) in a stirrer, 0.8g of lithium metal powder having a particle size of 40 μm was slowly added to the above solvent, adjusting the rotation speed to 1000rpm at room temperature, continuously stirring for reacting for 720min, stopping stirring, in a glove box protected by argon, the mixed solution is filtered by a Buchner funnel, light yellow solid powder is collected, then washing and filtering the lithium metal powder for three times by utilizing normal hexane to remove residual dimethyl sulfoxide to obtain dry lithium metal powder, the thickness of the passivation layer formed on the surface of the lithium metal powder is about 60nm, and fig. 3 is a transmission electron microscope image of the stabilized lithium powder prepared in this example, and it can be seen from the transmission electron microscope image that an obvious coating layer is formed on the surface of the lithium powder.
EXAMPLE 2
Adding 2g of ammonium bifluoride into a glass three-neck flask in argon atmosphere, adding 100mL of dimethyl sulfoxide solvent into the flask, rapidly stirring (500rpm) by a stirrer to fully dissolve the ammonium bifluoride, slowly adding 0.8g of metal lithium powder with the particle size of 40 mu m into the solvent, regulating the rotating speed to 1000rpm at room temperature, continuously stirring for reacting for 720min, stopping stirring, performing suction filtration on the mixed solution through a Buchner funnel in an argon-protected glove box to collect faint yellow solid powder, washing and filtering the metal lithium powder by using n-hexane for three times, removing residual dimethyl sulfoxide, and obtaining dry metal lithium powder, wherein the thickness of a passivation layer formed on the surface of the metal lithium powder is about 100 nm.
EXAMPLE 3
Adding 3g of ammonium bifluoride into a glass three-neck flask in argon atmosphere, adding 100mL of dimethyl sulfoxide solvent into the flask, rapidly stirring (500rpm) by a stirrer to fully dissolve the ammonium bifluoride, slowly adding 0.8g of metal lithium powder with the particle size of 25 mu m into the solvent, heating the flask to 60 ℃ by a heating sleeve, adjusting the rotation speed to 1000rpm, continuously stirring for reaction for 360min, stopping stirring, performing suction filtration on the mixed solution by a Buchner funnel in an argon-protected glove box, collecting faint yellow solid powder, washing and filtering the metal lithium powder by using n-hexane for three times, and removing residual dimethyl sulfoxide to obtain dry metal lithium powder, wherein the thickness of a passivation layer formed on the surface of the metal lithium powder is about 300 nm.
EXAMPLE 4
Adding 1kg of ammonium bifluoride into a stainless steel reaction kettle in an argon atmosphere, adding 2000m L dimethyl sulfoxide solvent into a bottle, fully dissolving the ammonium bifluoride by quickly stirring through a homogenizer (1000rpm), slowly adding 500g of metal lithium powder with the particle size of 40 mu m into the solvent, heating until the internal temperature of the stainless steel reaction kettle is 80 ℃, adjusting the rotation speed to 2000rpm at the temperature, continuously stirring for reaction for 180min, stopping stirring, performing suction filtration on the mixed solution through a Buchner funnel in an argon-protected glove box, collecting faint yellow solid powder, washing and filtering the metal lithium powder for three times by utilizing n-pentane, and removing residual dimethyl sulfoxide to obtain dry metal lithium powder, wherein the thickness of a passivation layer formed on the surface of the metal lithium powder is about 120 nm.
EXAMPLE 5
Adding 1g of potassium hydrogen fluoride into a glass three-neck flask under argon atmosphere, adding 100mL of acetone solvent into the flask, rapidly stirring by a stirrer (500rpm) to fully dissolve the potassium hydrogen fluoride, slowly adding 0.8g of metal lithium powder with the particle size of 25 mu m into the solvent, heating the flask to 60 ℃ by a heating sleeve, adjusting the rotation speed to 1000rpm at the temperature, continuously stirring for 360min, stopping stirring, performing suction filtration on the mixed solution by a Buchner funnel in an argon-protected glove box, collecting light yellow solid powder, washing and filtering the metal lithium powder by n-pentane for three times, and removing residual acetone to obtain dry metal lithium powder, wherein the thickness of a passivation layer formed on the surface of the metal lithium powder is about 80 nm.
EXAMPLE 6
Under argon atmosphere, adding 4g of sodium hydrogen fluoride into a glass three-neck flask, adding 100mL of propylene carbonate solvent into the flask, rapidly stirring by a stirrer (500rpm) to fully dissolve potassium hydrogen fluoride, slowly adding 0.8g of metal lithium powder with the particle size of 25 micrometers into the solvent, heating the flask to 100 ℃ by a heating sleeve, adjusting the rotation speed to 1000rpm at the temperature, continuously stirring for reaction for 120min, stopping stirring, performing suction filtration on the mixed solution by a Buchner funnel in an argon-protected glove box, collecting light yellow solid powder, washing and filtering the metal lithium powder by petroleum ether for three times, removing residual propylene carbonate, and obtaining dry metal lithium powder, wherein the thickness of a passivation layer formed on the surface of the metal lithium powder is about 400 nm.
Comparative example 1
Adding 8g of ammonium bifluoride into a glass three-neck flask under argon atmosphere, adding 100mL of dimethyl sulfoxide solvent into the flask, stirring quickly (500rpm) by a stirrer to fully dissolve the ammonium bifluoride, slowly adding 0.8g of metal lithium powder with the particle size of 40 mu m into the solvent, regulating the rotating speed to 1000rpm at room temperature, continuously stirring for reacting for 720min, stopping stirring, performing suction filtration on the mixed solution through a Buchner funnel in an argon-protected glove box to collect light yellow solid powder, washing and filtering the metal lithium powder with n-hexane for three times, removing residual dimethyl sulfoxide, and obtaining dry metal lithium powder, wherein a thicker passivation layer is formed on the surface of the metal lithium powder, the thickness of the passivation layer is about 1.5 mu m, and the excessive fluorine source is serious.
Comparative example 2
Adding 0.4g of ammonium bifluoride into a glass three-neck flask in argon atmosphere, adding 100mL of dimethyl sulfoxide solvent into the flask, rapidly stirring (500rpm) by a stirrer to fully dissolve the ammonium bifluoride, slowly adding 0.8g of metal lithium powder with the particle size of 40 mu m into the solvent, adjusting the rotating speed to 1000rpm at room temperature, continuously stirring for reacting for 720min, stopping stirring, performing suction filtration on the mixed solution through a Buchner funnel in a glove box protected by argon to collect light yellow solid powder, washing and filtering the metal lithium powder by using n-hexane for three times, removing residual dimethyl sulfoxide, and obtaining dry metal lithium powder, wherein a complete lithium fluoride passivation layer is not formed on the surface of the metal lithium powder, and a bare layer exists on the surface of the lithium powder, which is caused by limited fluorine source.
Comparative example 3
Adding 1g of ammonium bifluoride into a glass three-neck flask under argon atmosphere, adding 100mL of dimethyl sulfoxide solvent into the flask, stirring quickly (500rpm) by a stirrer to fully dissolve the ammonium bifluoride, slowly adding 0.8g of metal lithium powder with the particle size of 40 microns into the solvent, regulating the rotation speed to 1000rpm at 150 ℃, continuously stirring for reacting for 720min, stopping stirring, performing suction filtration on the mixed solution through a Buchner funnel in an argon-protected glove box, collecting light yellow solid powder, washing and filtering the metal lithium powder for three times by using n-hexane, removing residual dimethyl sulfoxide, and obtaining dry metal lithium powder, wherein a coating layer grows unevenly, and a complete lithium fluoride passivation layer is not formed on the surface of the metal lithium powder, and the reaction is severe.
Comparative example 4
Adding 1g of ammonium bifluoride into a glass three-neck flask under argon atmosphere, adding 100mL of dimethyl sulfoxide solvent into the flask, stirring quickly (500rpm) by a stirrer to fully dissolve the ammonium bifluoride, slowly adding 0.8g of metal lithium powder with the particle size of 5 microns into the solvent, regulating the rotating speed to 1000rpm at room temperature, continuously stirring for reacting for 720min, stopping stirring, performing suction filtration on the mixed solution through a Buchner funnel in an argon-protected glove box to collect light yellow solid powder, washing and filtering the metal lithium powder with n-hexane for three times, removing residual dimethyl sulfoxide, and obtaining dry metal lithium powder, wherein a passivation layer formed on the surface of the metal lithium powder is limited and is not completely coated because the lithium powder has small particle size, high specific surface area and relatively few fluorine sources.
Comparative example 5
Under the atmosphere of argon, 1g of ammonium bifluoride is added into a glass three-neck flask, 100mL of dimethyl sulfoxide solvent is added into the flask, after ammonium bifluoride was sufficiently dissolved by rapid stirring (500rpm) in a stirrer, 0.8g of lithium metal powder having a particle size of 150 μm was slowly added to the above solvent, adjusting the rotation speed to 1000rpm at 150 ℃, continuously stirring for reacting for 720min, stopping stirring, in a glove box protected by argon, the mixed solution is filtered by a Buchner funnel, light yellow solid powder is collected, then washing and filtering the lithium metal powder for three times by utilizing normal hexane to remove residual dimethyl sulfoxide to obtain dry lithium metal powder, wherein the thickness of the passivation layer formed on the surface of the metal lithium powder is 200nm, although a uniform and compact lithium fluoride passivation layer is formed on the surface of the lithium powder, however, the lithium powder has large particle size and is difficult to be uniformly distributed on the surface of the pole piece, and excessive lithium supplement is easily caused in the pre-lithiation process.
Evaluation:
1. testing effective metal lithium and specific capacity:
passivated lithium metal powder and stabilized lithium powder with polymer coating prepared according to examples 1-3 were spread in petri dishes and left to stand in a drying room with humidity < 5% for 72 h.
After different standing times, respectively taking 20mg of the two powders, uniformly mixing the two powders with carbon black and polyvinylidene fluoride in N-methyl pyrrolidone according to the proportion of 7:2:1 to prepare lithium powder electrode slurry, coating the electrode slurry on copper foil by scraping, drying, cutting into pieces, weighing, preparing a lithium powder electrode, assembling a button cell by taking the copper foil as a counter electrode, and taking electrolyte containing 1M LiPF6A mixed solution of ethylene carbonate and diethyl carbonate (EC: DMC ═ 1: 1); and standing for 10 hours, carrying out constant current charging at 0.05C, carrying out a discharge capacity test at a cut-off voltage of 2V, recording the charge capacity, and calculating the effective gram capacity of the lithium powder according to the mass of the lithium powder deposited on the copper foil counter electrode.
The results are shown in fig. 4, and the stable lithium powder prepared by the method of the present invention has higher initial specific capacity compared to the capacity of the polymer-coated lithium powder; and the capacity loss after long-term storage is lower, which shows that the lithium metal powder prepared by the invention has better lithium utilization rate and stability.
2. First effect and cycle performance testing:
under the same conditions, the stable lithium metal powder prepared in examples 1 to 6 and comparative examples 1 to 5 is used for carrying out pre-lithiation on the negative plate, a battery is prepared (the preparation method is the same as evaluation 1), and the first effect and the cycle performance of the battery corresponding to different examples are tested under the same conditions. Specifically, the method comprises the following steps:
the preparation method of the pre-lithiation negative plate comprises the following steps:
(1) SiOx is used as a negative electrode active material, carbon black is used as a conductive agent, Styrene Butadiene Rubber (SBR) is used as a binder, sodium carboxymethylcellulose (CMC) is used as a dispersant, water is used as a solvent, and the raw materials are stirred and mixed uniformly to form negative electrode slurry;
(2) uniformly coating the mixed negative electrode slurry on the surface of copper foil, drying and rolling to obtain a negative electrode plate;
(3) dispersing the stable lithium powder prepared in examples 1-6 and comparative examples 1-5 in a N-methylpyrrolidone (NMP) solution containing 5% polyvinylidene fluoride (PVDF), and uniformly stirring to prepare a lithium powder slurry, wherein the solid content of the lithium powder is 5%;
(4) coating the lithium powder slurry on the surface of the prepared negative plate in a low-humidity environment, and performing vacuum drying and rolling on the coating with the thickness of 100 mu m to obtain a pre-lithiated negative plate;
(5) punching a non-pre-lithiated negative plate and a pre-lithiated negative plate, respectively assembling a button type half cell, standing for 24 hours, and carrying out first-effect and cycle performance tests, wherein the electrolyte is LiPF6：EC：DEC：PP＝1：1.78：3.57：1.4。
The parameters of the stable lithium powder pre-lithiated negative electrode sheet prepared in the examples 1 to 6 and the comparative examples 1 to 5, the first effect of the battery and the cycle performance test results are shown in table 1.
Table 1 results of the prelithiation test using the stabilized lithium powders obtained in examples 1 to 6 and comparative examples 1 to 5
According to the method for preparing the stable lithium powder, lithium fluoride which is low in solubility in water and can exist stably is used for coating the surface of the metal lithium powder to generate a continuous and dense passivation protective layer, and compared with the traditional metal lithium powder, the stable lithium powder has higher specific capacity, and the utilization rate of the metal lithium is greatly improved. The stable lithium powder prepared in the embodiments 1 to 6 is used for carrying out pre-lithiation on the silicon-oxygen negative plate, the stable lithium powder is used as exogenous lithium in the circulation process, a rapid lithium intercalation reaction is carried out on the surface of the negative plate, and a uniform and compact SEI film is preferentially consumed on the surface of the negative electrode, so that the consumption of positive active lithium is greatly reduced, and the initial efficiency and the circulation stability of the battery are greatly improved.
In addition, when the silicon-oxygen negative electrode sheet is subjected to pre-lithiation on the lithium powder prepared in the comparative examples 1-5, when the mass ratio of the lithium fluoride passivation layer to the lithium powder is too small, the passivation layer is too thin, the coating effect on the lithium powder is poor, the activity of the lithium powder is high, and the lithium powder is easy to react with water and oxygen in the air when exposed to the external environment, so that the lithium powder is rapidly oxidized and even ignited, the stability is poor, and the potential safety hazard is large; if the mass ratio of the lithium fluoride passivation layer to the lithium powder is too large, the passivation layer is thick, the content of metal lithium of the lithium powder added in the pre-lithiation process is low, the dissolution rate of the lithium powder is reduced, the effect of improving the first efficiency of the battery is not obvious, the effect of improving the capacity, the first effect and the cycling stability of the battery is poor, and even the inherent performance of the battery is influenced, when the mass ratio of the lithium fluoride passivation layer to the lithium powder is controlled to be (0.5-1.8): 1, the coating layer can be ensured to have proper thickness, the stability of the lithium powder is obviously improved, the stable use of the lithium powder in a low-humidity environment is realized, and meanwhile, the stable lithium powder is used for pre-lithiation, a lithium supplement layer can be formed on the surface of a pole piece in a dry-environment in a dry-method dispersion or wet-method dispersion mode, so that the.
In conclusion, the method disclosed by the invention is simple in process, and the prepared stable lithium powder has high stability and long storage life, so that the lithium powder is convenient to safely transport, store and use, and can be widely used as a lithium supplement additive of a lithium battery electrode material.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method of making a stabilized lithium powder, comprising: mixing and reacting fluorine-containing acid salt, lithium powder and an organic solvent to form a lithium fluoride passivation layer on the surface of the lithium powder so as to obtain stable lithium powder, wherein the mass ratio of the lithium fluoride passivation layer to the lithium powder in the stable lithium powder is (0.5-1.8): 1.
2. The method of claim 1, comprising:
(1) mixing and stirring the fluorine-containing acid salt and the organic solvent to obtain a fluorine source solution;
(2) mixing the lithium powder with the fluorine source solution under an inert atmosphere and heating and stirring the mixture so as to react the lithium powder with the fluorine source solution;
(3) and (3) filtering, cleaning and drying the product obtained in the step (2) so as to obtain the stable lithium powder with the surface provided with the lithium fluoride passivation layer.
3. The method according to claim 2, wherein in the step (2), the temperature of the heating and stirring is 25 to 120 ℃, the stirring speed is 500 to 2000rpm, and the time is 60 to 720min,
optionally, in the step (3), the filtration is performed by suction filtration with a buchner funnel or natural filtration with a filter screen, and the solvent used for washing is at least one selected from alkanes, alkenes and aromatic hydrocarbons with a boiling point of less than 150 ℃.
4. The method according to any one of claims 1 to 3, wherein the particle size of the lithium powder is 10 to 100 μm.
5. The method of claim 4, wherein the passivation layer has a thickness of 50 to 500 nm.
6. The method according to claim 1 or 5, wherein the mass ratio of the fluorine-containing acid salt to the lithium powder is (1-5): 1,
optionally, the fluorine-containing acid salt is at least one selected from the group consisting of ammonium bifluoride, sodium bifluoride and potassium bifluoride,
optionally, the organic solvent is at least one selected from the group consisting of dimethyl sulfoxide, acetone, dimethylformamide, dimethylacetamide, 1, 3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide, and propylene carbonate.
7. A stabilized lithium powder, characterized in that it is obtained by the process according to any one of claims 1 to 6.
8. The negative plate is characterized in that the preparation process comprises the following steps: prelithiation is performed using the stabilized lithium powder of claim 7 or the stabilized lithium powder prepared by the method of any one of claims 1 to 6.
9. The negative electrode plate of claim 8, wherein the negative electrode plate is a silicon-based negative electrode plate.
10. A lithium battery characterized by having the negative electrode sheet of claim 8 or 9.
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| CN113036106A (en) * | 2021-03-09 | 2021-06-25 | 昆山宝创新能源科技有限公司 | Composite lithium supplement additive and preparation method and application thereof |
| CN114388790A (en) * | 2020-10-21 | 2022-04-22 | 比亚迪股份有限公司 | Battery prelithiation slurry, battery negative plate and lithium ion battery |
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