CN113753870A - GeP nanosheet negative electrode for lithium ion battery and ultrasonic-assisted rapid stripping preparation method thereof - Google Patents
GeP nanosheet negative electrode for lithium ion battery and ultrasonic-assisted rapid stripping preparation method thereof Download PDFInfo
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Abstract
The invention provides an GeP nanosheet negative electrode for a lithium ion battery and an ultrasonic-assisted rapid stripping preparation method thereof, and the preparation method comprises the following steps: (1) weighing a tetrabutyl cation compound, dissolving the tetrabutyl cation compound in an organic solvent, and stirring for dissolving to obtain a saturated tetrabutyl cation stripping reagent; (2) taking a saturated tetrabutyl cation stripping reagent, taking GeP single crystal as a working electrode and a platinum electrode as a counter electrode, applying a voltage of 2.2-3.0V, and simultaneously carrying out ultrasonic treatment for 5-15 minutes; (3) pouring the solution obtained by stripping into a centrifugal tube, and centrifuging to obtain a deposit of the two-dimensional nanosheet; (4) re-dissolving the sediment of the two-dimensional nano-sheets in an ethanol solvent or deionized water; (5) finally, the obtained sediment of the two-dimensional nano-sheets is re-dissolved in an ethanol solvent or deionized water, and is sealed and stored to obtain the dispersion liquid of the two-dimensional nano-sheets. The invention realizes the quick and effective stripping of GeP single crystal materials and the obtained product has high electrochemical performance.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to an GeP nanosheet negative electrode for a lithium ion battery and an ultrasonic-assisted rapid stripping preparation method thereof.
Background
The two-dimensional layered nano material refers to a nano material with a nano size in one dimension, and the two-dimensional layered material which is widely researched at present is prepared by peeling GeP single crystal material of a three-dimensional matrix of the two-dimensional layered nano material. Taking graphene and graphite as examples, graphene is separated from layered graphite by applying mechanical force to the layered graphite. The bulk lamellar graphite is bonded by strong C-C bonds in the layer surface, and orderly stacked and arranged between layers only by virtue of Van der Waals force, so that the effective peeling of the lamellar structure material is realized after the Van der Waals force between the layers is overcome by external force. Two-dimensional (2D) layered nanomaterials widely studied at present, such as graphene (graphene), Boron Nitride (BN), molybdenum disulfide (MoS)2) And the like, all prepared by peeling off three-dimensional parent single crystal materials.
GeP have been studied and paid attention as a new layered nanomaterial in recent years, however, peeling of a two-dimensional GeP nanosheet is difficult to peel as fast and efficient as graphite due to its small interlayer spacing and large van der waals force. The existing two-dimensional material preparation method comprises a mechanical peeling method (tape hand peeling) and a liquid phase peeling method (ultrasonic treatment is carried out by adding solvents such as ethanol, acetone and the like), and is widely applied to preparing thin-layer materials in laboratories, but the method has the disadvantages of long time consumption (generally >24 hours or even days), low yield (yield < 5%), difficulty in controlling the size and the layer thickness of the prepared crystals, incapability of controllably preparing two-dimensional materials with proper length and thickness, and difficulty in industrial production. Meanwhile, the liquid phase stripping method leads to the rise of the temperature of the solvent due to the introduction of the organic solvent and the long-time ultrasound, which often leads to the oxidation failure of the two-dimensional material product, and the organic functional groups loaded on the surface are difficult to remove, thereby greatly reducing the purity of the product.
Disclosure of Invention
In view of the above, the invention provides an ultrasonic-assisted rapid stripping preparation method of GeP nanosheet negative electrodes for lithium ion batteries, which overcomes the defects of the prior art.
The technical scheme of the invention is realized as follows:
an ultrasonic-assisted rapid stripping preparation method of GeP nanosheet negative electrodes for lithium ion batteries comprises the following steps:
(1) weighing a tetrabutyl cation compound, dissolving the tetrabutyl cation compound in an organic solvent, and stirring for dissolving to obtain a saturated tetrabutyl cation stripping reagent; the stripping agent provides a tetrabutyl cation concentration high enough to ensure effective intercalation and exfoliation of GeP single crystal material;
(2) taking the saturated tetrabutyl cation stripping reagent in the step (1), taking GeP single crystal as a working electrode and a platinum electrode as a counter electrode, applying a voltage of 2.2-3.0V, and simultaneously carrying out ultrasonic treatment at a power of 50-150W and a temperature of 25-60 ℃ for 5-15 minutes to carry out electrochemical tetrabutyl cation intercalation stripping;
the reason for "applying a voltage of 2.2-3.0V" in this step is to ensure effective intercalation and exfoliation of tetrabutyl cations, too low a working voltage (<2.2V) and too small an electrochemical driving force cannot intercalate tetrabutyl cations into GeP interlamination, while too high a working voltage (>3V) and too large an electrochemical driving force can intercalate tetrabutyl cations too fast, resulting in shattering and exfoliation of GeP single crystal material, and effective exfoliation cannot be achieved; in a voltage range of 2.2-3.0V, GeP single crystal materials can be effectively peeled, and the peeling time is faster and the time consumption is short as the voltage is increased, but the peeled GeP nano-sheets become thicker, the size is smaller, and the uniformity is slightly worse.
In the step, the ultrasonic power is 50-150W and the ultrasonic temperature is 25-60 ℃, so that the GeP single crystal material is better assisted to be effectively embedded and stripped, and the shattering or oxidation of a nanosheet product is avoided. The GeP component is completely peeled off in a very short time, and the peeled GeP nano flakes are fully and completely dispersed in the solution.
(3) Pouring the solution obtained by stripping in the step (2) into a centrifugal tube, and centrifuging for 25-35 minutes by adopting a centrifugal machine at a high rotating speed of 9000-11000 r/min to obtain the sediment of the two-dimensional nano sheet;
in the step, the centrifugal condition can well separate the two-dimensional GeP nano-flakes from the solution completely, because the GeP nano-flakes are light and thin, the GeP nano-flakes can be separated from the tetrabutylammonium iodide solution by centrifugation at a high enough rotating speed for a long enough centrifugation time;
(4) re-dissolving the sediment of the two-dimensional nano-sheets in the step (3) in an ethanol solvent or deionized water, and repeating the operation in the step (3), namely repeating the operations in the steps (3) - (4) for 2-3 times; the' repeated operation is to wash GeP nano-flakes to sufficiently wash away tetrabutyl cations and iodide ions existing on the surface of GeP nano-flakes;
(5) finally, the obtained sediment of the two-dimensional nano-sheets is re-dissolved in an ethanol solvent or deionized water, and is sealed and stored to obtain the dispersion liquid of the two-dimensional nano-sheets.
Further, in the step (1), the tetrabutyl cation compound is at least one of tetrabutyl ammonium iodide and tetrabutyl ammonium phosphate.
Further, in the step (1), the organic solvent is dimethylformamide.
Further, the mass volume ratio g/ml of the tetrabutyl cation compound to the organic solvent is 3.7 g: 20.
further, in the step (2), the ultrasonic power is 80W, and the ultrasonic temperature is 30 ℃.
Further, in the step (2), the reaction time is 10 minutes.
Further, in the step (3), the centrifugal rotating speed is 10000 rpm, and the centrifugal time is 30 minutes.
An GeP nanosheet negative electrode for a lithium ion battery is prepared by the preparation method provided by the invention.
Compared with the prior art, the invention has the beneficial effects that:
the GeP nanosheet negative electrode for the lithium ion battery and the ultrasonic-assisted rapid stripping preparation method thereof have the advantages of simple process, low cost, short time consumption, high yield, capability of batch synthesis preparation and easiness for large-scale production synthesis, and compared with the existing like products, the GeP nanosheet negative electrode for the lithium ion battery has the following advantages:
(1) compared with the defects of long time consumption (generally >24 hours or even days), low yield (yield < 5%) and uncontrollable product size and thickness of the traditional mechanical stripping method and liquid phase stripping method, the ultrasonic-assisted electrochemical cation intercalation stripping method provided by the invention realizes the rapid and effective stripping of GeP single crystal material (within 15 minutes), obtains the two-dimensional GeP nano material with controllable layer number and thickness and adjustable size and length, and has high yield (> 90%).
(2) The product prepared by the preparation method has high purity, the GeP nano-flake surface is not easy to be oxidized, other oxidation functional group impurities are not contained, the stability is good, and the purity is high;
(3) when the GeP nano-flake obtained by stripping preparation is applied to a lithium ion battery cathode material, the discharging capacity is larger, the reversibility is higher, the rate performance and the cycle stability are good, and the electrochemical performance is excellent.
(4) The invention has simple process, low cost and easy construction of the device.
Drawings
FIG. 1.GeP is a representation of the morphology of a single crystal mass;
FIG. 2 is a schematic view of the layered crystal structure and exfoliation of a single-crystal block of GeP;
FIG. 3 optical microscope images of GeP nanoflakes from the peel preparation;
FIG. 4 shows a scanning electron microscope atlas of GeP nano-sheets obtained by peeling and a corresponding distribution atlas of elements;
FIG. 5 Raman spectra of a bulk GeP before and after single crystal exfoliation;
FIG. 6 atomic force microscope thickness characterization of GeP nanoflakes obtained from the lift-off preparation;
FIG. 7 shows that GeP nano sheets obtained by peeling preparation are applied to electrochemical performance tests of lithium ion battery cathodes.
Detailed Description
In order to better understand the technical content of the invention, specific examples are provided below to further illustrate the invention.
The experimental methods used in the examples of the present invention are all conventional methods unless otherwise specified.
The materials, reagents and the like used in the examples of the present invention can be obtained commercially without specific description.
Example 1
1 the method comprises the following steps:
(1) solution preparation: 3.7g of tetrabutylammonium iodide (C) are weighed out13H13IN) is dissolved IN 20ml of Dimethylformamide (DMF) solution, and the solution is fully stirred and dissolved to obtain a saturated tetrabutylammonium iodide stripping agent;
(2) stripping: taking the saturated tetrabutylammonium iodide solution obtained in the step (1), taking GeP single crystal as a working electrode and a platinum electrode as a counter electrode, applying a voltage of 2.6V, and simultaneously carrying out ultrasonic treatment at a power of 80W and a temperature of 30 ℃ for 10 minutes to carry out electrochemical tetrabutyl cation intercalation stripping;
(3) centrifuging: pouring the solution obtained by stripping in the step (2) into a centrifugal tube, and centrifuging for 30 minutes by adopting a centrifuge at a high rotating speed of 10000 r/min to obtain a deposit of a two-dimensional GeP nano sheet;
(4) washing: re-dissolving the sediment of the two-dimensional GeP nano flakes in the deionized water in the step (3), repeating the step (3) of centrifugation, and repeating the step (3) of centrifugation-step (4) of washing operation for 2 times to fully wash away tetrabutyl cations and iodide ions in the solution;
(5) sealing and storing: and (4) dissolving the deposit of the two-dimensional GeP nano-sheets obtained at the end of the step (5) in deionized water again, sealing and storing to obtain the dispersion of the two-dimensional GeP nano-sheets.
2 Performance test
2.1 the GeP single crystal of the invention is synthesized by a Flux fusion method, the morphology and structure of the GeP single crystal block are characterized as shown in fig. 1, and the morphology and structure of the block can be observed by a scanning electron microscope, so that the block can be found to be a layered structure which is orderly stacked and arranged, and the layers are tightly stacked by van der waals force. Raman tests show that the peak position of a Raman vibration signal of the material is consistent with the characteristic peak of GeP, and an element distribution mapping map also detects the uniform distribution of Ge elements and P elements, so that the successful synthesis of the pure-phase bulk GeP single crystal material is proved.
2.2GeP layered crystal structure of single crystal block and schematic diagram of peeling are shown in fig. 2, where GeP single crystal is used as working electrode, platinum electrode is used as counter electrode, ultrasonic-assisted electrochemical tetrabutyl cation intercalation peeling is performed, tetrabutyl cation (TBAP) is rapidly embedded into interlayer spacing of GeP single crystal block under the action of working voltage, ultrasonic wave and electrochemical driving force, and van der waals force between layers is overcome, thereby realizing effective peeling of GeP single crystal block.
2.3 optical microscope characterization of GeP nanosheets prepared by exfoliation, as shown in fig. 3, each GeP nanosheet was uniformly dispersed, indicating that GeP single crystal achieved effective exfoliation.
2.4, the GeP nano-flake prepared by peeling is characterized in appearance, as shown in fig. 4, the flake size is about 20 microns long and about 10 microns wide, the element is analyzed, Ge and P elements can be uniformly distributed without other impurity elements from the EDS image, which indicates that the nano-flake prepared by peeling is GeP material in pure phase.
2.5 comparing with fig. 5, it can be seen that the peeled GeP nanosheets maintain Raman vibration mode as same as bulk, which indicates that the original phase structure of the GeP nanosheets is not changed after peeling, and the stability is good, and the nanosheets are not oxidized by iodine elementary substance as a counter electrode product in the peeling process, and can be stably stored and placed in air or ethanol solution.
2.6 atomic force microscopy thickness characterization of GeP nanoflakes prepared by exfoliation showed that, as shown in fig. 6, exfoliated GeP nanoflakes are substantially about 19 nanometers thick (about 0.8 nanometers for a monolayer GeP), corresponding to about 20 multilayers of GeP.
2.7 the GeP nano-sheets obtained by peeling were applied to the negative electrode material of lithium ion batteries for battery assembly and electrochemical performance testing, and the results are shown in fig. 7. In the graph of FIG. 7(a), the first discharge capacity of the GeP nano-flake is as high as 1780mAh/g, the first charge capacity is about 1200mAh/g, and the reversibility is high. The dQ/dV spectrum in fig. 7(b) shows that the charging and discharging platforms corresponding to the dQ/dV peak positions (redox peaks) are all below 0.5V, and the GeP nanosheets on the surface have a relatively low charging and discharging potential, and are suitable for being used as a negative electrode material of a lithium ion battery. Even at high current densities of up to 2000mA/g [ fig. 7(c) -7(d) ], the reversible discharge capacity of the GeP nanoflakes was as high as 400mAh/g, indicating good rate capability. After 120 cycles [ fig. 7(e) ], the residual reversible capacity of the GeP nanoflakes was still 468mAh/g, indicating good cycle life and stability.
Example 2
On the basis of the embodiment 1, the process of the step (2) is adjusted, and specifically, the method comprises the following steps: taking the saturated tetrabutylammonium iodide solution obtained in the step (1), using GeP single crystal as a working electrode and a platinum electrode as a counter electrode, applying a voltage of 2.2V, and simultaneously carrying out ultrasonic treatment at a power of 50W and a temperature of 25 ℃ for reaction for 15 minutes to carry out electrochemical tetrabutyl cation intercalation stripping. The other conditions were the same as in example 1.
The results show that the reduction of applied voltage and ultrasonic power greatly slows the rate of exfoliation of GeP single crystal, that after 15 minutes of reaction, a complete exfoliation of the remaining bulk material on the GeP single crystal working electrode is not achieved, that the exfoliation process slows down, and that the yield of the reaction product is reduced. However, the obtained GeP nano thin sheet has thinner thickness, basically about 10 nm, larger size, more uniform size and better quality.
Example 3
On the basis of the embodiment 1, the process of the step (2) is adjusted, and specifically, the method comprises the following steps: taking the saturated tetrabutylammonium iodide solution obtained in the step (1), taking GeP single crystal as a working electrode and a platinum electrode as a counter electrode, applying a voltage of 3.0V, and simultaneously carrying out ultrasonic treatment at a power of 150W and a temperature of 60 ℃ for 5 minutes to carry out electrochemical tetrabutyl cation intercalation stripping. The other conditions were the same as in example 1.
The results show that the increase of the applied voltage and the ultrasonic power can greatly improve the peeling rate of GeP single crystal, and after 5 minutes of reaction, the bulk material on the GeP single crystal working electrode can be completely peeled, the peeling process is obviously accelerated, and the peeling efficiency is higher. However, the GeP nm flakes obtained were thicker, essentially about 30 nm thick, smaller in size, somewhat less uniform and somewhat less overall in quality.
Example 4
On the basis of the embodiment 1, the process of the step (3) is adjusted, and specifically, the method comprises the following steps: pouring the solution obtained by stripping in the step (2) into a centrifugal tube, and centrifuging for 35 minutes by adopting a high rotating speed of 9000 revolutions per minute of a centrifuge to obtain a deposit of two-dimensional GeP nano flakes. The other conditions were the same as in example 1.
The results show that GeP nanoflakes can be sedimented and separated from the dispersion by appropriate reduction of the rotation speed and appropriate extension of the centrifugation time, resulting in a sediment of GeP nanoflakes comparable to example 1.
Example 5
On the basis of the embodiment 1, the process of the step (3) is adjusted, and specifically, the method comprises the following steps: pouring the solution obtained by stripping in the step (2) into a centrifugal tube, and centrifuging for 25 minutes at a high rotating speed of 11000 r/min by using a centrifuge to obtain the sediment of the two-dimensional GeP nano flakes. The other conditions were the same as in example 1.
The results showed that GeP nanoflakes could also be sedimented and separated from the dispersion by a suitable increase in the rotation speed and a suitable reduction in the centrifugation time, resulting in a sediment of GeP nanoflakes comparable to that of example 1.
Comparative example 1
On the basis of example 1, the stripping process lacks ultrasonic assistance, and the other steps are not subjected to ultrasound. The method specifically comprises the following steps: and (2) taking the saturated tetrabutylammonium iodide solution obtained in the step (1), applying a voltage of 2.6V to the working electrode which is GeP single crystal and the counter electrode which is platinum electrode, and carrying out electrochemical tetrabutyl cation intercalation stripping. The other conditions were the same as in example 1.
The results show that the peeling effect and efficiency of the GeP single crystal material are obviously reduced, the complete peeling of the residual bulk material on the GeP single crystal working electrode is not realized, the peeling process is slowed down, and the yield of the reaction product is reduced. And in the subsequent centrifugal washing process, if a subsequent ultrasonic dispersion step is lacked, the deposited GeP nano-sheets cannot be re-dispersed in deionized water or DMF solution, and the GeP nano-sheets can be seriously agglomerated into blocks, so that GeP nano-sheets cannot be obtained.
Comparative example 2
On the basis of example 1, the stripping process was carried out without ultrasonic assistance, and ultrasonic dispersion was carried out after washing. The method specifically comprises the following steps: (1) 3.7g of tetrabutylammonium iodide (C) are weighed out13H13IN) is dissolved IN 20mL of Dimethylformamide (DMF) solution, and the solution is fully stirred and dissolved to obtain saturated tetrabutylammonium iodide solution;
(2) taking the saturated tetrabutylammonium iodide solution obtained in the step (1), taking GeP single crystal as a working electrode and a platinum electrode as a counter electrode, applying a voltage of 2.6V, reacting for 10 minutes, and performing electrochemical tetrabutyl cation intercalation stripping;
(3) pouring the solution obtained by stripping in the step (2) into a centrifugal tube, and centrifuging for 30 minutes by adopting a centrifuge at a high rotating speed of 10000 r/min to obtain a deposit of a two-dimensional GeP nano sheet;
(4) re-dissolving the sediment of the two-dimensional GeP nano flakes in the deionized water in the step (3), repeating the step (3) of centrifugation, and repeating the step (3) of centrifugation-step (4) of washing operation for 2 times to fully wash away tetrabutyl cations and iodide ions in the solution;
(5) and (4) dissolving the deposit of the two-dimensional GeP nano-sheets obtained at the end of the step (5) in deionized water again, performing ultrasonic dispersion at the power of 80W and the temperature of 30 ℃, sealing and storing to obtain the dispersion liquid of the two-dimensional GeP nano-sheets.
The results show that the peeling effect and efficiency of the GeP single crystal material are obviously reduced, the complete peeling of the residual bulk material on the GeP single crystal working electrode is not realized, the peeling process is slowed down, and the yield of the reaction product is reduced. This is because, absent the assistance of ultrasound, the GeP nanosheets that were peeled off could not be separated from the electrode into the solution in time, and were concentrated and surrounded near the electrode, hindering the subsequent intercalation of tetrabutyl cations and the peeling process, which would prolong the peeling time and reduce the peeling process and efficiency. However, if the ultrasonic dispersion step is performed in the subsequent centrifugal washing process, the GeP nano-flakes which have been peeled off can be well dispersed in deionized water or DMF solution, and can be effectively preserved, and a small amount of two-dimensional GeP nano-flake dispersion liquid is obtained.
Comparative example 3
On the basis of example 1, the stripping operation operating voltage was adjusted.
The method specifically comprises the following steps: taking the saturated tetrabutylammonium iodide solution obtained in the step (1), taking GeP single crystal as a working electrode and a platinum electrode as a counter electrode, applying a voltage of 5.0V, and simultaneously carrying out ultrasonic treatment at a power of 80W and a temperature of 30 ℃ for 10 minutes and 10 minutes to carry out electrochemical tetrabutyl cation intercalation stripping. The other processes were in accordance with example 1.
The results show that the excessively high working voltage causes the tetrabutyl cation intercalation rate to be excessively fast, which directly causes the pulverization and the falling of GeP single crystal material, GeP single crystal is pulverized and refined into a plurality of fine crystal grains to be deposited at the bottom of the solution before stripping, the effective stripping of the single crystal cannot be realized, and the two-dimensional GeP nano thin slice cannot be obtained.
Comparative example 4
On the basis of example 1, the ultrasonic process conditions were adjusted.
The method specifically comprises the following steps: taking the saturated tetrabutylammonium iodide solution obtained in the step (1), using GeP single crystal as a working electrode and a platinum electrode as a counter electrode, applying a voltage of 2.6V, and simultaneously carrying out ultrasonic treatment at a power of 200W and a temperature of 70 ℃ for 10 minutes to carry out electrochemical tetrabutyl cation intercalation stripping. The other processes were in accordance with example 1.
The result shows that the ultrasonic power is too high, the originally stripped two-dimensional GeP nanosheets are shattered, a large number of holes appear on the surfaces of the GeP nanosheets, the nanosheets are shattered into more fine nanosheets, and the original smooth and complete two-dimensional nanosheet shape is not maintained; and the two-dimensional GeP nano-sheets which are originally stripped can be oxidized by the excessively high ultrasonic temperature (70 ℃), a large number of oxygen-containing functional groups are introduced to the surface, and a large number of side reactions occur, so that the oxidative decomposition of the GeP nano-sheets is caused.
Comparative example 5
On the basis of example 1, the centrifugation process conditions were adjusted.
The method specifically comprises the following steps: pouring the solution obtained by stripping in the step (2) into a centrifugal tube, and centrifuging for 60 minutes by adopting a centrifuge at a high rotating speed of 5000 revolutions per minute to obtain the sediment of the two-dimensional nano-sheets. The other processes were in accordance with example 1.
The results show that too low a rotational speed does not provide sufficient centrifugal force to fully deposit all GeP nanoflakes, resulting in substantially less, if not almost no, deposits, and a greatly reduced yield of GeP nanoflakes.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, 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 (8)
1. An ultrasonic-assisted rapid stripping preparation method of GeP nanosheet negative electrodes for lithium ion batteries is characterized by comprising the following steps:
(1) weighing a tetrabutyl cation compound, dissolving the tetrabutyl cation compound in an organic solvent, and stirring for dissolving to obtain a saturated tetrabutyl cation stripping reagent;
(2) taking the saturated tetrabutyl cation stripping reagent in the step (1), taking GeP single crystal as a working electrode and a platinum electrode as a counter electrode, applying a voltage of 2.2-3.0V, and simultaneously carrying out ultrasonic treatment at a power of 50-150W and a temperature of 25-60 ℃ for 5-15 minutes to carry out electrochemical tetrabutyl cation intercalation stripping;
(3) pouring the solution obtained by stripping in the step (2) into a centrifugal tube, and centrifuging for 25-35 minutes by adopting a centrifugal machine at a high rotating speed of 9000-11000 r/min to obtain the sediment of the two-dimensional nano sheet;
(4) re-dissolving the sediment of the two-dimensional nano-sheets in the step (3) in an ethanol solvent or deionized water, and repeating the operation in the step (3), namely repeating the operations in the steps (3) - (4) for 2-3 times;
(5) finally, the obtained sediment of the two-dimensional nano-sheets is re-dissolved in an ethanol solvent or deionized water, and is sealed and stored to obtain the dispersion liquid of the two-dimensional nano-sheets.
2. The method according to claim 1, wherein in the step (1), the tetrabutyl cationic compound is at least one of tetrabutylammonium iodide and tetrabutylammonium phosphate.
3. The method according to claim 2, wherein in the step (1), the organic solvent is dimethylformamide.
4. The preparation method according to claim 3, wherein in the step (1), the mass-to-volume ratio g/ml of the tetrabutyl cation compound to the organic solvent is 3.7 g: 20.
5. the production method according to claim 4, wherein in the step (2), the ultrasonic power is 80W, and the ultrasonic temperature is 30 ℃.
6. The production method according to claim 5, wherein the reaction time in the step (2) is 10 minutes.
7. The method according to claim 6, wherein in the step (3), the centrifugation rotation speed is 10000 rpm, and the centrifugation time is 30 minutes.
8. GeP nanosheet negative electrode for a lithium ion battery, characterized by being prepared by the preparation method of any one of claims 1 to 6.
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