CN113753870B - GeP nano-sheet negative electrode for lithium ion battery and ultrasonic-assisted rapid stripping preparation method thereof - Google Patents
GeP nano-sheet negative electrode for lithium ion battery and ultrasonic-assisted rapid stripping preparation method thereof Download PDFInfo
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Abstract
The invention provides a GeP nano-sheet negative electrode for a lithium ion battery and an ultrasonic-assisted rapid stripping preparation method thereof, which comprise the following steps: (1) Weighing tetrabutyl cation compound, dissolving in an organic solvent, and stirring to dissolve to obtain a saturated tetrabutyl cation stripping reagent; (2) Taking saturated tetrabutyl cation stripping reagent, taking GeP monocrystal as a working electrode, taking a platinum electrode as a counter electrode, applying 2.2-3.0V voltage, and simultaneously carrying out ultrasonic treatment and reacting for 5-15 minutes; (3) Pouring the stripped solution into a centrifuge tube, and centrifuging to obtain a sediment of the two-dimensional nano-sheet; (4) Redissolving the two-dimensional nano-flake deposit in an ethanol solvent or deionized water; (5) And finally, redissolving the obtained sediment of the two-dimensional nano-flakes in an ethanol solvent or deionized water, and sealing and preserving to obtain a dispersion liquid of the two-dimensional nano-flakes. The method realizes the rapid and effective stripping of the GeP monocrystalline material, and the obtained product has high electrochemical performance.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a GeP nanometer sheet negative electrode for a lithium ion battery and an ultrasonic-assisted rapid stripping preparation method thereof.
Background
The two-dimensional layered nano material is nano material with nano size in one dimension, and the two-dimensional layered material widely studied at present is prepared by stripping GeP single crystal material of a three-dimensional matrix. Taking graphene and graphite as examples, graphene is obtained by applying mechanical force to lamellar graphite to separate the lamellar material. The block lamellar graphite is bonded by strong C-C bonds in the layers, and orderly stacked and arranged between layers only by virtue of Van der Waals force, so that effective stripping of lamellar structure materials is realized after the interlayer Van der Waals force is overcome by external force. Two-dimensional (2D) layered nanomaterials, such as graphene (graphene), boron Nitride (BN), molybdenum disulfide (MoS) 2 ) And the like are prepared by stripping three-dimensional matrix single crystal materials.
GeP has recently been studied and focused as a novel layered nanomaterial, however, exfoliation of a two-dimensional GeP nanosheet is difficult to be rapidly and effectively exfoliated as graphite due to its small interlayer spacing and large van der Waals force. The existing two-dimensional material preparation methods comprise a mechanical stripping method (tape hand stripping) and a liquid phase stripping method (ultrasonic treatment by adding solvents such as ethanol and acetone) and are widely applied to preparing thin-layer materials in a laboratory, but the method takes a long time (usually more than 24 hours and even up to several days) and has low yield (the yield is less than 5%), the prepared crystal size and layer thickness are not easy to control, and the prepared two-dimensional material with proper length and thickness cannot be controllably prepared and is difficult to be applied to industrial production. Meanwhile, the liquid phase stripping method often causes oxidation failure of a two-dimensional material product due to the introduction of an organic solvent and the increase of the solvent temperature caused by long-time ultrasonic treatment, a large amount of organic functional groups on the surface are difficult to remove, and the purity of the product is greatly reduced.
Disclosure of Invention
In view of the above, the invention provides an ultrasonic-assisted rapid stripping preparation method of GeP nanometer sheet cathodes 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 a GeP nanometer negative electrode for a lithium ion battery comprises the following steps:
(1) Weighing tetrabutyl cation compound, dissolving in an organic solvent, and stirring to dissolve to obtain a saturated tetrabutyl cation stripping reagent; the stripping agent provides a tetrabutyl cation concentration high enough to ensure effective intercalation and stripping of GeP single crystal material;
(2) Taking the saturated tetrabutyl cation stripping reagent in the step (1), taking GeP monocrystal as a working electrode, taking a platinum electrode as a counter electrode, applying a voltage of 2.2-3.0V, simultaneously carrying out ultrasonic treatment at the power of 50-150W and the temperature of 25-60 ℃ for 5-15 minutes, and carrying out electrochemical tetrabutyl cation intercalation stripping;
in the step, the voltage of 2.2-3.0V is applied to ensure effective intercalation and exfoliation of tetrabutyl cations, the tetrabutyl cations cannot be intercalated into GeP layer spacing due to a too low working voltage (< 2.2V) and too small electrochemical driving force, and the tetrabutyl cations can be intercalated too quickly due to a too high working voltage (> 3V) and too large electrochemical driving force, so that GeP single crystal materials are crushed and exfoliated, and effective exfoliation cannot be realized; in the voltage interval of 2.2-3.0V, the GeP monocrystalline material can be effectively stripped, and along with the voltage lifting, the stripping time is faster and the time consumption is shorter, but the GeP nanometer sheet stripped is thicker, smaller in size and slightly worse in uniformity.
In the step, ultrasonic power of 50-150W and ultrasonic temperature of 25-60 ℃ better assist in effectively embedding and stripping GeP monocrystalline materials, and the nanosheet products are prevented from being broken or oxidized. The GeP component is peeled off in a very short time, and the GeP nanometer flake peeled off is fully and completely dispersed in the solution.
(3) Pouring the solution stripped in the step (2) into a centrifuge tube, and centrifuging at a high rotation speed of 9000-11000 r/min for 25-35 min by adopting the centrifuge to obtain a sediment of the two-dimensional nano-sheet;
the centrifugation conditions in this step can better separate the two-dimensional GeP nanoflakes from the solution because GeP nanoflakes are very light and thin, and the GeP nanoflakes can be centrifuged from the tetrabutylammonium iodide solution at a sufficiently high rotational speed and for a sufficiently long centrifugation time;
(4) Redissolving the sediment of the two-dimensional nano sheet in the step (3) in 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; this "repeat operation was to wash GeP nanoflakes to sufficiently wash away the tetrabutyl cations and iodide ions present on the GeP nanoflakes surface;
(5) And finally, redissolving the obtained sediment of the two-dimensional nano-flakes in an ethanol solvent or deionized water, and sealing and preserving to obtain a dispersion liquid of the two-dimensional nano-flakes.
Further, in the step (1), the tetrabutyl cationic 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 cationic compound to the organic solvent is 3.7g: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 speed is 10000 revolutions per minute, and the centrifugal time is 30 minutes.
A GeP nanometer piece negative electrode for a lithium ion battery, which is prepared by the preparation method of any one of the invention.
Compared with the prior art, the invention has the beneficial effects that:
the GeP nano-sheet negative electrode for the lithium ion battery and the ultrasonic-assisted rapid stripping preparation method thereof provided by the invention have the advantages of simple process, low cost, short time consumption, high yield, batch synthesis and preparation, and easiness in mass production and synthesis, and compared with the existing similar products, the method provided by the invention has the following advantages:
(1) Compared with the traditional mechanical stripping method and liquid phase stripping method which take long time (usually more than 24 hours and even up to several days), have low yield (yield < 5%), and uncontrollable product size and thickness, the ultrasonic assisted electrochemical cation intercalation stripping method provided by the invention realizes rapid and effective stripping (within 15 minutes) of GeP single crystal material, and obtains the two-dimensional GeP nano material with controllable layer number and thickness and adjustable size and length, and the yield is high (> 90%).
(2) The product prepared by the preparation method has high purity, geP nano-sheet surface is not easy to oxidize, does not contain other oxidized functional group impurities, has good stability and has higher purity;
(3) The GeP nano sheet prepared by stripping has larger discharge capacity, higher reversibility, good rate capability and cycle stability and excellent electrochemical performance when being applied to a lithium ion battery anode material.
(4) The invention has simple process, low cost and easy construction of the device.
Drawings
FIG. 1. Topographical structural characterization of GeP single crystal blocks;
FIG. 2. Layered crystal structure and exfoliation schematic of GeP single crystal bulk;
FIG. 3 is an optical microscope image of GeP nanoflakes prepared by stripping;
FIG. 4 shows a GeP nanometer thin sheet scanning electron microscope map and a corresponding element distribution map obtained by stripping;
FIG. 5 Raman spectrum of the block GeP single crystal before and after exfoliation;
FIG. 6 atomic force microscope thickness characterization of GeP nanoflakes prepared by exfoliation;
fig. 7. Electrochemical performance test of the GeP nanoflakes prepared by the stripping applied to the negative electrode of the lithium ion battery.
Detailed Description
In order to better understand the technical content of the present invention, the following provides specific examples to further illustrate the present invention.
The experimental methods used in the embodiment of the invention are conventional methods unless otherwise specified.
Materials, reagents, and the like used in the examples of the present invention are commercially available unless otherwise specified.
Example 1
The specific steps of 1 are as follows:
(1) Preparing a solution: 3.7g of tetrabutylammonium iodide (C) 13 H 13 IN) is dissolved IN 20ml of Dimethylformamide (DMF) solution, and fully stirred and dissolved to obtain saturated tetrabutylammonium iodide stripping agent;
(2) Stripping: taking saturated tetrabutylammonium iodide solution in the step (1), taking GeP monocrystal as a working electrode, taking a platinum electrode as a counter electrode, applying 2.6V voltage, simultaneously carrying out ultrasonic treatment at the power of 80W and the temperature of 30 ℃ for 10 minutes, and carrying out electrochemical tetrabutyl cation intercalation stripping;
(3) And (3) centrifuging: pouring the solution obtained in the step (2) into a centrifuge tube, and centrifuging for 30 minutes at a high rotation speed of 10000 revolutions per minute by adopting the centrifuge to obtain a sediment of the two-dimensional GeP nanometer sheet;
(4) Washing: redissolving the sediment of the two-dimensional GeP nano sheet in the step (3) in deionized water, repeating the centrifugal operation in the step (3), and repeating the centrifugal operation in the step (3) -the washing operation in the step (4) for 2 times so as to fully wash out tetrabutyl cations and iodide ions in the solution;
(5) Sealing: and (3) redissolving the sediment of the two-dimensional GeP nano-thin sheet obtained in the step (5) in deionized water, sealing and preserving to obtain a dispersion liquid of the two-dimensional GeP nano-thin sheet.
2 Performance test
2.1 the GeP single crystal of the invention is synthesized by a Flux melting method, the morphology structure of the GeP single crystal block is characterized in that the morphology structure is shown in figure 1, and the ordered stacked layered structure can be found by observing the morphology structure through a scanning electron microscope, and layers are closely stacked by Van der Waals force between the layers. The Raman test shows that the Raman vibration signal peak position is consistent with the characteristic peak of GeP, the element distribution mapping map also detects the uniform distribution of Ge element and P element, and the successful synthesis of the pure-phase block GeP single crystal material is proved.
2.2GeP the layered crystal structure and the stripping schematic diagram of the single crystal block are shown in fig. 2, geP single crystal is used as a working electrode, a platinum electrode is used as a counter electrode, ultrasonic assisted electrochemical tetrabutyl cation intercalation stripping is carried out, tetrabutyl cation (TBAP) is rapidly embedded into the interlayer spacing of the block GeP single crystal under the action of working voltage, ultrasonic waves and electrochemical driving force, and interlayer van der Waals force is overcome, so that the effective stripping of the GeP single crystal block is realized.
2.3 optical microscopy characterization of the GeP nanoflakes prepared by exfoliation, as shown in fig. 3, each GeP nanoflakes were uniformly dispersed, indicating that the GeP single crystal achieved effective exfoliation.
2.4 morphology characterization was performed on the GeP nanoflakes prepared by exfoliation, as shown in fig. 4, the flake size was about 20 microns long and about 10 microns wide, and analysis of the elements showed that the Ge and P elements were uniformly distributed and no other impurity elements from EDS images, indicating that the nanoflakes prepared by exfoliation were pure phase GeP material.
2.5 As can be seen from the comparison of FIG. 5, the peeled GeP nanosheets maintain the Raman vibration mode as that of the block, which shows that the original phase structure of the peeled GeP nanosheets is not changed, the stability is good, the peeled nanosheets are not oxidized by the iodine simple substance of the counter electrode product in the peeling process, and the peeled nanosheets can be stably stored in air or ethanol solution.
2.6 atomic force microscopy thickness characterization of the GeP nanoflakes from the peel preparation, as shown in fig. 6, the peel GeP nanoflakes were substantially 19 nanometers thick (about 0.8 nanometers for monolayer GeP) with about 20 multilayers of corresponding GeP.
2.7 the GeP nano-sheets prepared by stripping are applied to a lithium ion battery cathode material, and the battery assembly and electrochemical performance test are carried out, and the result is shown in fig. 7. In FIG. 7 (a), the first discharge capacity of the GeP nano-sheet is up to 1780mAh/g, and the first charge capacity is about 1200mAh/g, so that the reversibility is high. In fig. 7 (b), the dQ/dV spectrum shows that the peak position (redox peak) of the dQ/dV is below 0.5V, and the GeP nano-sheet has a low charge-discharge potential, which is suitable for use as a negative electrode material of a lithium ion battery. Even at high current densities up to 2000mA/g [ fig. 7 (c) -7 (d) ], the reversible discharge capacity of GeP nanoflakes was as high as 400mAh/g, indicating good rate performance. After 120 cycles [ fig. 7 (e) ] the remaining reversible capacity of the GeP nanoflakes is still 468mAh/g, indicating good cycle life and stability.
Example 2
Based on the embodiment 1, the process of the step (2) is adjusted, specifically: taking saturated tetrabutylammonium iodide solution in the step (1), taking GeP monocrystal as a working electrode, taking a platinum electrode as a counter electrode, applying 2.2V voltage, simultaneously carrying out ultrasonic treatment at the power of 50W and the temperature of 25 ℃ for 15 minutes, and carrying out electrochemical tetrabutyl cation intercalation stripping. Other conditions were the same as in example 1.
The results show that the reduction in applied voltage and ultrasonic power greatly slowed the peeling rate of GeP single crystals, and after 15 minutes of reaction, the remaining portion of bulk material on the GeP single crystal working electrode did not completely peel, the peeling process slowed, and the yield of reaction products was reduced. However, the obtained GeP nanometer thin sheet is thinner, the thickness is basically about 10 nanometers, the size is larger and more uniform, and the quality is better.
Example 3
Based on the embodiment 1, the process of the step (2) is adjusted, specifically: taking saturated tetrabutylammonium iodide solution in the step (1), taking GeP monocrystal as a working electrode, taking a platinum electrode as a counter electrode, applying a voltage of 3.0V, simultaneously carrying out ultrasonic treatment at the power of 150W and the temperature of 60 ℃ for 5 minutes, and carrying out electrochemical tetrabutyl cation intercalation stripping. Other conditions were the same as in example 1.
The results show that the increase of the applied voltage and ultrasonic power can greatly increase the peeling rate of the GeP single crystal, and after 5 minutes of reaction, the bulk material on the GeP single crystal working electrode is completely peeled off, so that the peeling process is obviously accelerated, and the peeling efficiency is higher. However, the obtained GeP nanometer thin sheet has a thicker thickness of about 30 nanometers, a smaller size, slightly poorer uniformity and slightly poorer overall quality.
Example 4
Based on the embodiment 1, the process of the step (3) is adjusted, specifically: pouring the solution obtained in the step (2) into a centrifuge tube, and centrifuging for 35 minutes at a high rotation speed of 9000 rpm to obtain a deposit of the two-dimensional GeP nanometer sheet. Other conditions were the same as in example 1.
The results showed that GeP nanoflakes can be deposited and separated from the dispersion by appropriate reduction of the rotational speed and appropriate extension of the centrifugation time, resulting in a deposit of two-dimensional GeP nanoflakes comparable to example 1.
Example 5
Based on the embodiment 1, the process of the step (3) is adjusted, specifically: pouring the solution obtained in the step (2) into a centrifuge tube, and centrifuging at a high rotation speed of 11000 r/min for 25 min to obtain a sediment of the two-dimensional GeP nano-sheet. Other conditions were the same as in example 1.
The results showed that GeP nanoflakes can also be deposited and separated from the dispersion by a suitable increase in the rotational speed and a suitable reduction in the centrifugation time, resulting in a deposit of two-dimensional GeP nanoflakes comparable to example 1.
Comparative example 1
Based on example 1, the stripping process lacks ultrasound assistance and no other steps are performed. The method comprises the following steps: taking the saturated tetrabutylammonium iodide solution in the step (1), taking GeP monocrystal as a working electrode, taking a platinum electrode as a counter electrode, applying a voltage of 2.6V, and reacting for 10 minutes to perform electrochemical tetrabutyl cation intercalation stripping. Other conditions were the same as in example 1.
The results show that the peeling effect and efficiency of GeP single crystal material are obviously reduced, the residual part of the bulk material on the GeP single crystal working electrode is not completely peeled off, the peeling process is slowed down, and the yield of reaction products is reduced. And in the subsequent centrifugal washing process, if the subsequent ultrasonic dispersion step is absent, the deposited GeP nano-sheets cannot be redispersed in deionized water or DMF solution, and can be seriously agglomerated into blocks, so that GeP nano-sheets cannot be obtained.
Comparative example 2
Based on example 1, the stripping process was devoid of ultrasonic assistance and ultrasonic dispersion was performed after washing. The method comprises the following steps: (1) 3.7g of tetrabutylammonium iodide (C) 13 H 13 IN) IN 20mL of dimethylformamideFully stirring and dissolving in an amine (DMF) solution to obtain a saturated tetrabutylammonium iodide solution;
(2) Taking the saturated tetrabutylammonium iodide solution in the step (1), taking GeP monocrystal as a working electrode, taking 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 in the step (2) into a centrifuge tube, and centrifuging for 30 minutes at a high rotation speed of 10000 revolutions per minute by adopting the centrifuge to obtain a sediment of the two-dimensional GeP nanometer sheet;
(4) Redissolving the sediment of the two-dimensional GeP nano sheet in the step (3) in deionized water, repeating the centrifugal operation in the step (3), and repeating the centrifugal operation in the step (3) -the washing operation in the step (4) for 2 times so as to fully wash out tetrabutyl cations and iodide ions in the solution;
(5) Redissolving the sediment of the two-dimensional GeP nano-thin sheet obtained in the step (5) in deionized water, performing ultrasonic dispersion at the power of 80W and the temperature of 30 ℃, sealing and preserving to obtain a dispersion liquid of the two-dimensional GeP nano-thin sheet.
The results show that the peeling effect and efficiency of GeP single crystal material are obviously reduced, the residual part of the bulk material on the GeP single crystal working electrode is not completely peeled off, the peeling process is slowed down, and the yield of reaction products is reduced. The GeP nano-sheets which are peeled off cannot be timely separated from the electrode and enter the solution due to the lack of ultrasonic assistance, are concentrated around the electrode, and prevent subsequent embedding and peeling processes of tetrabutyl cations, so that the peeling time can be prolonged, and the peeling process and efficiency are reduced. 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, so that effective preservation is obtained, and a small amount of two-dimensional GeP nano-flake dispersion is obtained.
Comparative example 3
Based on example 1, the peeling operation operating voltage was adjusted.
The method comprises the following steps: taking the saturated tetrabutylammonium iodide solution in the step (1), taking GeP monocrystal as a working electrode, taking a platinum electrode as a counter electrode, applying a voltage of 5.0V, simultaneously carrying out ultrasonic treatment at the power of 80W and the temperature of 30 ℃, reacting for 10 minutes, and carrying out electrochemical tetrabutyl cation intercalation stripping. Other processes were consistent with example 1.
The result shows that the excessively high working voltage makes the intercalation rate of the tetrabutyl cation excessively high, directly causes the pulverization and the shedding of the GeP monocrystalline material, and the GeP monocrystalline is pulverized and refined into a plurality of fine grains to be deposited at the bottom of the solution before the pulverization and the shedding, so that the effective exfoliation of the monocrystalline can not be realized, and the two-dimensional GeP nanometer flake can not be obtained.
Comparative example 4
On the basis of example 1, the ultrasound process conditions were adjusted.
The method comprises the following steps: taking saturated tetrabutylammonium iodide solution in the step (1), taking GeP monocrystal as a working electrode, taking a platinum electrode as a counter electrode, applying 2.6V voltage, simultaneously carrying out ultrasonic treatment at the power of 200W and the temperature of 70 ℃ for 10 minutes, and carrying out electrochemical tetrabutyl cation intercalation stripping. Other processes were consistent with example 1.
The result shows that the ultrasonic power is too high, the originally peeled two-dimensional GeP nano-sheet is crushed, a large number of holes are formed in the surface of the GeP nano-sheet, and the holes are crushed into more fine nano-sheets, so that the original smooth and complete two-dimensional nano-sheet morphology is not maintained; and the ultrasonic temperature (70 ℃) is too high to oxidize the two-dimensional GeP nano-thin sheet which is stripped originally, a large amount of oxygen-containing functional groups are introduced into the surface, a large amount of side reactions occur, and the oxidative decomposition of the GeP nano-thin sheet is caused.
Comparative example 5
On the basis of example 1, the centrifugation process conditions were adjusted.
The method comprises the following steps: pouring the solution obtained by stripping in the step (2) into a centrifuge tube, and centrifuging for 60 minutes at a high rotation speed of 5000 revolutions per minute by adopting the centrifuge to obtain the sediment of the two-dimensional nano-sheet. Other processes were consistent with example 1.
The results show that too low a rotational speed does not provide sufficient centrifugal force to deposit all of the GeP nanoflakes, resulting in significantly reduced or even almost no deposits of the two-dimensional nanoflakes, greatly reducing the yield of GeP nanoflakes.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (7)
1. The ultrasonic-assisted rapid stripping preparation method of the GeP nanometer sheet negative electrode for the lithium ion battery is characterized by comprising the following steps of:
(1) Weighing tetrabutyl cation compound, dissolving in an organic solvent, and stirring to dissolve to obtain a saturated tetrabutyl cation stripping reagent;
(2) Taking the saturated tetrabutyl cation stripping reagent in the step (1), taking GeP monocrystal as a working electrode, taking a platinum electrode as a counter electrode, applying 2.6V voltage, simultaneously carrying out ultrasonic treatment at the power of 50-150W and the temperature of 25-60 ℃ for 5-15 minutes, and carrying out electrochemical tetrabutyl cation intercalation stripping;
(3) Pouring the solution stripped in the step (2) into a centrifuge tube, and centrifuging at a high rotation speed of 9000-11000 r/min for 25-35 min by adopting the centrifuge to obtain a sediment of the two-dimensional nano-sheet;
(4) Redissolving the sediment of the two-dimensional nano sheet in the step (3) in 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) And finally, redissolving the obtained sediment of the two-dimensional nano-flakes in an ethanol solvent or deionized water, and sealing and preserving to obtain a dispersion liquid of the two-dimensional nano-flakes.
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. A process according to claim 3, characterized in that in step (1), the mass to volume ratio g/ml of tetrabutylcationic compound to organic solvent is 3.7g:20.
5. the method according to claim 4, wherein in the step (2), the ultrasonic power is 80W and the ultrasonic temperature is 30 ℃.
6. The 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 centrifugal rotational speed is 10000 rpm and the centrifugal time is 30 minutes.
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