CN115663166A - Metal lithium composite material and preparation method thereof, negative electrode plate, lithium battery and electric device - Google Patents
Metal lithium composite material and preparation method thereof, negative electrode plate, lithium battery and electric device Download PDFInfo
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Abstract
The invention relates to a metal lithium composite material, a preparation method thereof, a negative pole piece, a lithium battery and an electric device. The metal lithium composite material comprises metal lithium, and graphene roll and graphene oxide which are dispersed in the metal lithium. The graphene roll and the graphene oxide form a uniform conductive network in the metal lithium, so that the uniform diffusion of lithium ions is facilitated. The metal lithium composite material has better stability and better lithium ion diffusion uniformity, is not easy to generate lithium dendrite when used as a negative pole piece, and can improve the electrochemical performance and the safety performance of a lithium battery.
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a metal lithium composite material and a preparation method thereof, a negative pole piece, a lithium battery and an electric device.
Background
Batteries are ubiquitous in our daily lives, and are supplied from energy sources of aerospace and electric vehicles to energy sources of electronic devices such as notebook computers and smart phones for storage. The lithium battery has revolutionary changes in products in the fields of transportation and communication by virtue of high energy density and ultra-long cycle performance, and becomes the most common energy storage system. Although lithium batteries are now approaching the theoretical limit, the demand for large energy storage systems and power batteries is still not met.
Lithium metal is very high in its theoretical specific capacity (3862 mAh g) -1 ) Low weight density (0.53 g cm) -3 ) The lowest reduction potential (-3.04V compared to the standard hydrogen electrode) was widely studied as the negative electrode of the next generation high energy density rechargeable battery. However, lithium metal as a negative electrode material is very likely to generate lithium dendrite or dead lithium, which greatly affects the capacity exertion and safety performance.
Disclosure of Invention
Based on the above, the invention provides the metal lithium composite material and the preparation method thereof, which can improve the stability and the lithium ion diffusion uniformity of the metal lithium material, and have better electrochemical performance and safety performance when used as a negative pole piece.
In addition, the invention also provides a negative pole piece, a lithium battery and an electric device comprising the metal lithium composite material.
In one aspect of the present invention, a lithium metal composite material is provided, including lithium metal, a graphene roll, and graphene oxide; the graphene roll and the graphene oxide are dispersed in the lithium metal.
In some embodiments, the mass ratio of the graphene roll, the graphene oxide, and the lithium metal is (1~4): (0.2 to 1): 10.
in some embodiments, the mass ratio of the graphene roll to the graphene oxide is (1~5): 1.
in some embodiments, the number of graphene oxide layers is 1 to 10.
In some embodiments, the graphene oxide has a single-layer sheet diameter of 5 μm to 100 μm.
In some embodiments, the method for preparing the graphene roll comprises the following steps:
dispersing graphene oxide in a solvent to prepare a graphene oxide dispersion;
cooling and solidifying the graphene oxide dispersion into a solid state at-200 to-180 ℃;
freeze-drying the solid graphene oxide dispersion, removing the solvent, and preparing a graphene oxide roll;
and reducing the graphene oxide roll to prepare the graphene roll.
In another aspect of the present invention, a method for preparing the lithium metal composite material is also provided, which includes the following steps:
mixing graphene roll and graphene oxide to prepare a mixture;
mixing the mixture with molten lithium metal to produce an intermediate;
and cooling and solidifying the intermediate to prepare the lithium metal composite material.
In another aspect of the invention, a negative electrode plate is also provided, which is characterized by comprising the metal lithium composite material.
In another aspect of the invention, a lithium battery is also provided, which includes the above negative electrode plate.
In another aspect of the invention, an electric device is also provided, which comprises the lithium battery.
The metal lithium composite material comprises metal lithium, and graphene roll and graphene oxide dispersed in the metal lithium. The graphene roll and the graphene oxide form a uniform conductive network in the metal lithium, so that the uniform diffusion of lithium ions is facilitated. The metal lithium composite material has better stability and better lithium ion diffusion uniformity, is not easy to generate lithium dendrite when used as a negative pole piece, and can improve the electrochemical performance and the safety performance of a lithium battery.
Drawings
Fig. 1 is a diagram of a lithium metal composite provided in example 1 of the present invention;
FIG. 2 is a voltage plateau test of lithium to a battery prepared separately in example 1 of the present invention and comparative example 1;
fig. 3 shows the specific discharge capacity of 600 cycles of the lithium batteries respectively prepared in example 1 and comparative example 1 according to the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the present invention, the technical features described in the open type include a closed technical solution composed of the listed features, and also include an open technical solution including the listed features. The terms "comprising" and "including" as used herein mean open or closed unless otherwise specified. For example, the terms "comprising" and "comprises" may mean that other components not listed may also be included or included, or that only listed components may be included or included.
In the present invention, the numerical intervals are regarded as continuous, and include the minimum and maximum values of the range and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
The percentage contents referred to in the present invention mean, unless otherwise specified, mass percentages for solid-liquid mixing and solid-solid phase mixing, and volume percentages for liquid-liquid phase mixing.
The percentage concentrations referred to in the present invention refer to the final concentrations unless otherwise specified. The final concentration refers to the ratio of the additive component in the system to which the component is added.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or a treatment within a certain temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
The invention provides a metal lithium composite material, which comprises metal lithium, graphene roll and graphene oxide; the graphene roll and the graphene oxide are dispersed in the lithium metal.
Graphene roll is a new graphene material, the structure of which is between one-dimensional and two-dimensional, and is a rolled nanocarbon material similar to carbon nanotubes. The edges of the graphene are not closed, and lithium ion migration is facilitated due to the open structure between the two ends of the graphene and the rolling layers. The surface of Graphene Oxide (GO) has rich oxygen-containing functional groups, the graphene oxide has excellent lithium affinity, the affinity between the graphene oxide and graphene roll is high, and the graphene roll and metal lithium can be uniformly dispersed, so that the stability of the composite material and the lithium ion diffusion uniformity can be improved.
The metal lithium composite material comprises metal lithium, and graphene roll and graphene oxide dispersed in the metal lithium. The graphene roll and the graphene oxide form a uniform conductive network in the metal lithium, so that the uniform diffusion of lithium ions is facilitated. Through the synergistic effect of the components, the metal lithium composite material has better stability and better lithium ion diffusion uniformity, is not easy to generate lithium dendrite when used as a negative pole piece, and can improve the electrochemical performance and the safety performance of a lithium battery.
In some embodiments, the mass ratio of the graphene roll, the graphene oxide, and the lithium metal is (1~4): (0.2 to 1): 10. the mass ratio of the components is within the range, and the composite material has better stability and lithium ion diffusion uniformity. Alternatively, the mass ratio of graphene roll, graphene oxide and metallic lithium is 2.
In some embodiments, the mass ratio of the graphene roll to the graphene oxide is (1~5): 1. the mass ratio of the graphene roll to the graphene oxide is controlled within the range, so that the graphene roll and the graphene oxide have better dispersibility and stability in the composite material, and a conductive network with better conductivity can be formed in the composite material. Optionally, the mass ratio of the graphene roll to the graphene oxide is 1:1, 2:1, 3:1, 4:1, 5:1, or any range of the above numerical compositions.
In some embodiments, the number of graphene oxide layers is 1 to 10. The number of layers of graphene oxide can be observed by an Atomic Force Microscope (AFM). Optionally, the number of graphene oxide layers is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or any range of the above.
In some embodiments, the graphene oxide has a single-layer sheet diameter of 5 μm to 100 μm. The monolayer sheet diameter of the graphene oxide can be observed by a Transmission Electron Microscope (TEM). Alternatively, the graphene oxide has a single layer sheet diameter of 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, or any combination thereof.
In some embodiments, the method for preparing the graphene roll comprises the following steps S110 to S140.
Step S110: and dispersing graphene oxide in a solvent to prepare a graphene oxide dispersion.
In some of the embodiments, the graphene oxide is dispersed in the solvent by ultrasound in step S110. In some of these embodiments, the solvent is water.
In some of these embodiments, the concentration of graphene oxide in the graphene oxide dispersion is 0.8 mg/mL to 0.9 mg/mL. Alternatively, the concentration of graphene oxide in the graphene oxide dispersion is 0.8 mg/mL, 0.82 mg/mL, 0.84 mg/mL, 0.85 mg/mL, 0.86 mg/mL, 0.88 mg/mL, or 0.9 mg/mL.
Step S120: and cooling and solidifying the graphene oxide dispersion into a solid state at-200 to-180 ℃.
In some of these embodiments, the graphene oxide dispersion is placed in liquid nitrogen in step S120 to be rapidly cooled to a solid state.
Step S130: and (4) freeze-drying the solid graphene oxide dispersion, removing the solvent, and preparing the graphene oxide roll.
Step S140: and reducing the graphene oxide roll to prepare the graphene roll.
In some of these embodiments, the graphene oxide roll is reduced by reaction with sodium nitrite. Specifically, the graphene oxide roll is dispersed in water, mixed with sodium nitrite and reacted at 85-95 ℃ for 1.5-2.5 h. And after the reaction is finished, centrifugally washing the precipitate by using deionized water, removing residual impurities, and drying to obtain the graphene roll.
In another embodiment of the present invention, a method for preparing the lithium metal composite material is also provided, which includes the following steps S210 to S230.
Step S210: and mixing the graphene roll and the graphene oxide to prepare a mixture.
In some embodiments, the mass ratio of the graphene roll to the graphene oxide is (1~4): (0.2 to 1). Further, the mass ratio of the graphene roll to the graphene oxide is (1~5): 1.
step S220: the mixture was mixed with molten lithium metal to prepare an intermediate.
In some of these embodiments, step S220 is performed under a protective atmosphere. Further, the protective atmosphere is nitrogen, argon or a mixture thereof. Specifically, step S220 is performed in a glove box.
In some of these embodiments, the molten lithium metal is prepared by heating a lithium foil or lithium powder at 250 ℃ to 350 ℃. Further, the heating temperature is 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 320 ℃, 330 ℃, 340 ℃ or 350 ℃.
Step S230: and cooling and solidifying the intermediate to prepare the metal lithium composite material.
The preparation method of the metal lithium composite material is obtained by mixing the graphene roll, the graphene oxide and the molten metal lithium, and cooling and solidifying, and is simple in preparation process, low in production cost and beneficial to large-scale industrial production. The prepared metal lithium composite material is used for the lithium battery negative pole piece and has better electrochemical performance and safety performance.
In another embodiment of the invention, a negative electrode plate is also provided, which includes the metal lithium composite material. The metal lithium composite material can be directly used as a negative pole piece of a lithium battery, can effectively inhibit the lithium dendrite problem of a metal lithium negative pole, and has higher capacity and safety.
In some of these embodiments, the negative electrode sheet does not contain a binder, a conductive agent, or other additives.
The metal lithium composite material has a self-supporting characteristic, and has better conductivity when being used as a negative pole piece, so that the negative pole piece does not need to be added with a binder, a conductive agent or other additives, and the energy density of the negative pole piece is further improved.
In another embodiment of the present invention, a lithium battery is further provided, including the above negative electrode plate.
Generally, a lithium battery includes a positive electrode tab, a negative electrode tab, an electrolyte, and a separator. During the charging and discharging process of the lithium battery, lithium ions are inserted and extracted back and forth between the positive pole piece and the negative pole piece. The electrolyte plays a role in conducting ions between the positive pole piece and the negative pole piece. The isolating film is arranged between the positive pole piece and the negative pole piece to prevent the short circuit of the positive pole and the negative pole.
In another embodiment of the present invention, an electric device is also provided, which includes the above lithium battery.
In some embodiments, the powered device includes a mobile phone, a tablet computer, a notebook computer, an electric vehicle, an electric bicycle, an energy storage device, and the like.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The following detailed description is given with reference to specific examples. The following examples are not specifically described, and other components except inevitable impurities are not included. Reagents and instruments used in the examples are all conventional in the art and are not specifically described. The experimental procedures, in which specific conditions are not indicated in the examples, were carried out according to conventional conditions, such as those described in the literature, in books, or as recommended by the manufacturer.
Example 1
The present embodiment provides a metallic lithium composite material. The preparation method comprises the following steps:
preparing a graphene roll: graphene oxide (single layer, sheet diameter of 0.5-5 μm) is dispersed in water, and ultrasonic treatment is carried out on the graphene oxide (single layer, sheet diameter of 0.5-5 μm) for 1 h, so as to obtain 80 mL 0.84 mg/mL graphene oxide dispersion. And (3) placing the graphene oxide dispersion in liquid nitrogen, rapidly cooling and solidifying to a solid state, taking out, and removing water by using a freeze dryer to obtain the graphene oxide roll. Graphene oxide rolls were dispersed in 150 mL water, 0.34 g sodium nitrite was added and the reaction 2 h was stirred at 90 ℃. And after the reaction is finished, centrifugally washing with deionized water, and drying to obtain the graphene roll.
Preparing a metal lithium composite material: according to the mass ratio of the graphene roll to the graphene oxide (single layer, sheet diameter of 0.5-5 μm) to the metal lithium of 2:0.5:10 preparing the raw material. And uniformly mixing the graphene roll and the graphene oxide. The heating plate was heated to 350 ℃ in a glove box, and a lithium metal foil was added and melted to obtain molten lithium metal. Adding the mixture of the graphene roll and the graphene oxide into molten metal lithium while heating and stirring to uniformly disperse the graphene roll and the graphene oxide, then cooling and solidifying to obtain the metal lithium composite material, and cutting the metal lithium composite material into wafers with the diameter of 15 mm and the thickness of 1 mm by using a die for later use. The lithium metal composite material prepared in this example can be seen in fig. 1.
Example 2
The present embodiment provides a lithium metal composite material, which is different from embodiment 1 in that the mass ratio of graphene roll, graphene oxide (single layer, sheet diameter 0.5 μm to 5 μm), and lithium metal is 1.5.
Example 3
The present embodiment provides a lithium metal composite material, which is different from embodiment 1 in that the mass ratio of graphene roll, graphene oxide (single layer, sheet diameter 0.5 μm to 5 μm), and lithium metal is 1.
Example 4
The present embodiment provides a lithium metal composite material, which is different from embodiment 1 in that the mass ratio of graphene roll, graphene oxide (single layer, sheet diameter 0.5 μm to 5 μm), and lithium metal is 2.
Example 5
The present embodiment provides a lithium metal composite material, which is different from embodiment 1 in that the mass ratio of the graphene roll, the graphene oxide (single layer, sheet diameter of 0.5 μm to 5 μm), and the lithium metal is 1.
Example 6
The present embodiment provides a lithium metal composite material, which is different from embodiment 1 in that the mass ratio of graphene roll, graphene oxide (single layer, sheet diameter of 0.5 μm to 5 μm), and lithium metal is 4.
Comparative example 1
The present comparative example provides a commercially available lithium sheet (Tianjin lithium industries, ltd., > 99.9%).
Comparative example 2
The present comparative example provides a lithium metal composite, which is different from example 3 in that the graphene roll is not included. The preparation method comprises the following steps: according to the mass ratio of graphene oxide (single layer, sheet diameter of 0.5-5 μm) to metal lithium of 2:10 preparing the raw material. The heating plate was heated to 350 ℃ in a glove box, and a lithium metal foil was added and melted to obtain molten lithium metal. Adding graphene oxide into molten metal lithium, heating and stirring the mixture at the same time to uniformly disperse the graphene oxide, then cooling and solidifying the mixture to obtain the metal lithium composite material, and cutting the metal lithium composite material into a wafer with the diameter of 15 mm and the thickness of 1 mm by using a die for later use.
Comparative example 3
This comparative example provides a lithium metal composite that is different from example 3 in that graphene oxide is not included. The preparation method comprises the following steps: according to the mass ratio of the graphene roll to the metal lithium being 2:10 preparing the raw material. The heating plate was heated to 350 ℃ in a glove box, and a lithium metal foil was added and melted to obtain molten lithium metal. Adding the graphene roll into molten metal lithium while heating and stirring to uniformly disperse the graphene roll, then cooling and solidifying to obtain the metal lithium composite material, and cutting the metal lithium composite material into a wafer with the diameter of 15 mm and the thickness of 1 mm by using a die for later use.
Comparative example 4
This comparative example provides a lithium metal composite that differs from example 1 in that the graphene coils were replaced with single-walled carbon nanotubes (mclin, diameter < 2 nm, tube length 5 μm to 30 μm). The preparation method comprises the following steps: preparing raw materials according to the mass ratio of a single-walled carbon nanotube to graphene oxide (single-layer, sheet diameter of 0.5-5 μm) to metallic lithium of 1. And uniformly mixing the carbon nano tube and the graphene oxide. The heating plate was heated to 350 ℃ in a glove box, and a lithium metal foil was added and melted to obtain molten lithium metal. Adding a mixture of carbon nanotubes and graphene oxide into molten metal lithium, heating while stirring to uniformly disperse the carbon nanotubes and the graphene oxide, then cooling and solidifying to obtain a metal lithium composite material, and cutting the metal lithium composite material into a wafer with the diameter of 15 mm and the thickness of 1 mm by using a die for later use.
Comparative example 5
This comparative example provides a lithium metal composite material, which is different from example 1 in that graphene oxide is replaced with graphite oxide. The preparation method comprises the following steps: preparing raw materials according to the mass ratio of the graphene roll, the graphite oxide and the metallic lithium of 1. And uniformly mixing the graphene roll and the graphite oxide. The heating plate was heated to 350 ℃ in a glove box, and a lithium metal foil was added and melted to obtain molten lithium metal. Adding the mixture of the graphene roll and the graphite oxide into molten metal lithium while heating and stirring to uniformly disperse the graphene roll and the graphite oxide, then cooling and solidifying to obtain the metal lithium composite material, and cutting the metal lithium composite material into a wafer with the diameter of 15 mm and the thickness of 1 mm by using a die for later use.
Preparing a positive pole piece: and (2) coating slurry obtained by mixing and dispersing a positive active material lithium iron phosphate, a conductive agent acetylene black and a binder PVDF in NMP according to a mass ratio of 7.
And (3) isolation film: the PE porous polymer film is used as a separation film.
Preparing an electrolyte: in an argon atmosphere glove box with the water content of less than 10ppm, ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) which are equal in volume are mixed to obtain an organic solvent, and then 1mol/L LiPF6 is uniformly dissolved in the organic solvent to obtain the electrolyte.
Preparing a lithium ion battery: the metal lithium composite materials prepared in the embodiment 1~6 and the comparative example 1~5 are respectively used as negative electrode plates, the positive electrode plate, the isolating film and the negative electrode plate are laminated to form a battery cell, and the lithium ion battery is prepared through the processes of packaging, electrolyte injection, sealing, formation and capacity grading.
Test section
Testing a voltage platform:
two sheets of the lithium metal composite laminates prepared in example 1 were assembled into the lithium-pair battery of example 1. Two sheets of the metallic lithium electrode laminates prepared in comparative example 1 were assembled into a lithium-pair battery of comparative example 1.
The lithium pair batteries of example 1 and comparative example 1 were subjected to charge and discharge tests under the conditions of 1 mAh and 1 mA. The change of the voltage of the lithium-ion secondary battery of example 1 and comparative example 1 with respect to the charge and discharge time was recorded. The test results are shown in FIG. 2.
And (3) testing the specific discharge capacity:
the lithium ion batteries prepared in the above examples and comparative examples were subjected to charge and discharge tests at 1C rate, and the initial specific discharge capacity and the specific discharge termination capacity after 600 cycles of each lithium battery were recorded. See figure 3 and table 1 for test results.
Lithium dendrite condition observation:
and (3) performing 10 times of charge-discharge cycles on the lithium ion battery, then disassembling the lithium ion battery to obtain the lithium metal composite material, and observing the lithium dendrite condition on the surface of the lithium metal composite material subjected to 10 times of cycles through a scanning electron microscope. The test results are reported in table 1.
TABLE 1
Referring to fig. 2, it can be seen that the lithium-lithium pair cells prepared from the lithium metal composite materials of example and comparative example 1 have stable voltage plateau and better cycling stability during the charge and discharge cycles of 1000 h. While the lithium of comparative example 1 showed randomly large voltage swings to the cell, the voltage plateaus were less stable, probably due to the formation of unstable lithium-electrolyte interfaces on the surface of the pole pieces, and internal short circuits due to the presence of lithium dendrites.
Fig. 3 is a diagram showing electrochemical properties of the charge and discharge test of the lithium ion battery prepared in example 1 and comparative example 1. It can be seen that, compared with the lithium ion battery of comparative example 1, the lithium ion battery of example 1 not only has a higher specific discharge capacity, but also has no significant capacity fading after 600 cycles of charge and discharge, and the lithium ion battery has a higher capacity and a better cycle retention rate.
As can be seen from the relevant data in Table 1, the initial specific discharge capacity of the lithium ion battery prepared from the metal lithium composite material of example 1~6 is 165.2 mAh/g to 178.9 mAh/g, and the lithium ion battery has a higher initial specific discharge capacity. After 600 charge-discharge cycles, the specific discharge capacity of the lithium ion battery prepared in embodiment 1~6 is 151.2 mAh/g to 165.7 mAh/g, and the lithium ion battery has a high cycle capacity retention rate (88% to 94%). And after 10 charge and discharge cycles, the lithium ion battery prepared in example 1~6 has no obvious lithium dendrite on the surface of the lithium metal composite material, which shows that the lithium metal composite material provided in example 1~6 can significantly inhibit the formation of lithium dendrite.
Comparative example 1 the lithium ion battery prepared by using a commercially available lithium sheet had an initial specific discharge capacity of 157 mAh/g, a specific discharge capacity of 105.8 mAh/g after 600 charge-discharge cycles, and a cycle capacity retention rate of only 67%. It can be seen that the initial specific discharge capacity of the lithium ion battery prepared from the commercial lithium sheet of comparative example 1 is lower than that of example 1~6, the cycle capacity retention rate is also significantly lower than that of example 1~6, and the capacity attenuation of the lithium ion battery is obvious. After 10 charge-discharge cycles, the lithium ion battery of comparative example 1 observed a large amount of lithium dendrite formation on the surface of the lithium sheet, which not only resulted in capacity attenuation, but also had great threat to the safety performance of the lithium ion battery.
The composition of the metal lithium composite material of the comparative example 2~5 is different from that of the example 1~6, and the initial specific capacity of the prepared lithium ion battery is 158.5 mAh/g-165.3 mAh/g, which is lower than that of the lithium ion battery of the example 1~6; the specific discharge capacity after 600 times of charge-discharge circulation is 146.7 mAh/g-152 mAh/g, and the circulation capacity retention rate is similar to that of the embodiment 1~6. Lithium dendrite formation was observed on the surface of the lithium metal composite after 10 charge-discharge cycles for the lithium ion battery of comparative example 2~5.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the present invention as set forth in the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.
Claims (10)
1. The metal lithium composite material is characterized by comprising metal lithium, graphene roll and graphene oxide; the graphene roll and the graphene oxide are dispersed in the lithium metal.
2. The lithium metal composite of claim 1, wherein the graphene roll, the graphene oxide, and the lithium metal are present in a mass ratio of (1~4): (0.2 to 1): 10.
3. the lithium metal composite of claim 2, wherein the graphene roll and the graphene oxide are present in a mass ratio of (1~5): 1.
4. the lithium metal composite according to claim 1, wherein the number of graphene oxide layers is 1 to 10.
5. The lithium metal composite according to claim 1, wherein the graphene oxide has a single-layer sheet diameter of 5 to 100 μm.
6. The lithium metal composite of any one of claims 1~5, wherein the method of making the graphene coil comprises the steps of:
dispersing graphene oxide in a solvent to prepare a graphene oxide dispersion;
cooling and solidifying the graphene oxide dispersion into a solid state at-200 to-180 ℃;
freeze-drying the solid graphene oxide dispersion, removing the solvent, and preparing a graphene oxide roll;
and reducing the graphene oxide roll to prepare the graphene roll.
7. The method of making the lithium metal composite of any one of claims 1~6 comprising the steps of:
mixing graphene roll and graphene oxide to prepare a mixture;
mixing the mixture with molten lithium metal to produce an intermediate;
and cooling and solidifying the intermediate to prepare the metal lithium composite material.
8. A negative electrode tab comprising the lithium metal composite of any one of claims 1~6.
9. A lithium battery comprising the negative electrode sheet as claimed in claim 8.
10. An electric device comprising the lithium battery according to claim 9.
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