CN110078042B - Lithium-rich lithium iron phosphate material and preparation method and application thereof - Google Patents
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Abstract
The invention relates to a lithium-rich lithium iron phosphate material and a preparation method and application thereof, belonging to the technical field of materials. In the preparation process of the material, lithium iron phosphate is used as a raw material and assembled in a button battery, and then the lithium-rich lithium iron phosphate material is prepared by performing charge-discharge cycle on the button battery. The lithium-rich lithium iron phosphate material is in a micro-nano grade, has a good lattice structure, is coated on an electrode to form a working electrode, is used for constructing an NO electrochemical biosensor, can be used for directly growing cells, can detect NO molecules released by the cells in situ in real time, shows extremely high sensitivity and selectivity in actual detection, and has stable electrochemical performance and long cycle service life. The material has simple and convenient preparation process, low cost of raw materials and convenient commercial application.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a lithium-rich lithium iron phosphate material and a preparation method and application thereof.
Background
NO is a cellular messenger molecule that is produced by the action of Nitric Oxide Synthase (NOS) by L-arginine and oxygen, and that rapidly diffuses within cells or crosses cell membranes to perform the second messenger's task. It is involved in regulating vital activities such as metabolism, proliferation, differentiation and apoptosis of cells under normal concentration, but when the concentration is too high, cytopathy can be caused, abnormal cell death can be caused, and body diseases can be caused, wherein pathological changes related to central nervous system, cardiovascular system, urogenital system, gastrointestinal tract activity, immune process and the like are abnormal along with the increase of NO concentration. Therefore, in situ real-time detection of NO released from cells is important for exploring its diversity in biological systems.
The methods for detecting NO are various, including fluorescence, colorimetry, electrochemistry, chromatography and the like, wherein the electrochemistry has the advantages of simplicity, sensitivity, low cost, rapid detection and the like, so that an electrochemical sensor can be adopted to detect NO molecules in real time. However, the efficient electrochemical detection of NO mostly depends on the use of noble metal materials, and the cost is high, so that the method is not favorable for large-scale production and use. Therefore, the NO electrochemical sensor based on non-noble metal has huge application prospect.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing a lithium-rich lithium iron phosphate material; the other purpose is to provide a lithium-rich lithium iron phosphate material; it is a further object to provide an electrochemical sensor; the fourth purpose is to provide the application of the electrochemical sensor in NO detection.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a preparation method of a lithium-rich lithium iron phosphate material comprises the following steps:
(1) Adding lithium iron phosphate, conductive carbon black and polyvinylidene fluoride into N-methyl pyrrolidone, uniformly mixing to obtain a mixture, coating the mixture on an aluminum foil and drying to obtain an aluminum foil loaded with the lithium iron phosphate, taking the aluminum foil loaded with the lithium iron phosphate as a positive electrode, a metal lithium sheet as a counter electrode, a polyethylene microporous membrane as a diaphragm and a lithium hexafluorophosphate electrolyte as an electrolyte, and assembling to obtain the button battery;
(2) And (2) performing charge-discharge circulation on the button battery obtained in the step (1), then disassembling the button battery, taking out the positive electrode, cleaning and drying the positive electrode, and scraping the lithium-rich lithium iron phosphate material on the positive electrode.
Preferably, in the step (1), the mass ratio of the lithium iron phosphate to the conductive carbon black to the polyvinylidene fluoride is 4-9; the thickness of the aluminum foil is 160-180 mu M, the concentration of lithium hexafluorophosphate in the lithium hexafluorophosphate electrolyte is 1M, and the button cell is a CR250 type button cell.
Preferably, in the step (1), the drying is specifically drying at 110-120 ℃ for 10-12h.
Preferably, in the step (2), the charge-discharge cycle is specifically to discharge and then charge under the conditions that the voltage range is 2.0 +/-0.2V to 4.2 +/-0.3V, the current is 0.1-0.5C, and the temperature is 23-27 ℃, and the final state is to discharge to the lowest voltage after the cycle.
Preferably, in the step (2), the organic solution is used as a cleaning solution during cleaning, and the drying is specifically drying at 20-80 ℃ for 2-5h.
2. The lithium-rich lithium iron phosphate material prepared by the method.
3. An electrochemical sensor comprises an electrochemical workstation, a working electrode, a counter electrode, a reference electrode, an electrolytic cell and electrolyte, wherein the surface of the working electrode is coated with the lithium-rich lithium iron phosphate material.
Preferably, the working electrode is prepared by the following method:
dispersing the lithium-rich lithium iron phosphate material in water according to the proportioning concentration of 2.8-3.8mg/mL to obtain an electrode modification solution, coating the electrode modification solution on an electrode, and drying.
Preferably, the drying is specifically drying at 20-100 ℃ for 20-60min.
4. The use of said electrochemical sensor for the detection of NO.
The invention has the beneficial effects that: the invention provides a lithium-rich lithium iron phosphate material, a preparation method and application thereof, wherein the lithium-rich lithium iron phosphate material is in a micro-nano grade in size and has a good lattice structure, and is coated on an electrode to form a working electrode for constructing an NO electrochemical biosensor. The material has simple and convenient preparation process, low cost of raw materials and convenient commercial application.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims thereof.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
fig. 1 is a scanning electron microscope image and a perspective electron microscope image of the lithium-rich lithium iron phosphate material prepared in example 1; (in FIG. 1, a is a scanning electron microscope, and in FIG. 1, b is a transmission electron microscope)
FIG. 2 is an X-ray diffraction pattern of the lithium-rich lithium iron phosphate material prepared in example 1;
fig. 3 is a scanning electron microscope image and a perspective electron microscope image of the lithium-rich lithium iron phosphate material prepared in example 2; (in FIG. 3, a is a scanning electron microscope, and in FIG. 3, b is a transmission electron microscope.)
FIG. 4 is an X-ray diffraction pattern of the lithium-rich lithium iron phosphate material prepared in example 2;
fig. 5 is a scanning electron microscope image and a perspective electron microscope image of the lithium-rich lithium iron phosphate material prepared in example 3; (in FIG. 5, a is a scanning electron microscope, and in FIG. 5, b is a transmission electron microscope)
FIG. 6 is an X-ray diffraction pattern of the lithium-rich lithium iron phosphate material prepared in example 3;
fig. 7 is a graph showing the results of testing the lithium ion content of the lithium iron phosphate material discharged to different voltages in example 1;
FIG. 8 is a graph of the results of cyclic voltammetric response tests of the sensor constructed in example 1 to NO at a voltage range of-0.2-1.1V;
FIG. 9 is a graph of the results of a timed current response test to NO at 0.85V for a sensor constructed in example 1;
FIG. 10 is a graph of the NO concentration versus current response obtained from FIG. 9;
FIG. 11 is a graph showing the results of the selectivity test of the sensor constructed in example 1 for different interfering components;
FIG. 12 is a graph showing the results of the sensor stability test constructed in example 1;
FIG. 13 is a graph showing the results of current response tests of the sensor constructed in example 1 for NO detection of cells grown directly on the electrodes and cells in the culture dish.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
Preparing lithium-rich lithium iron phosphate material, coating working electrode of the material and constructing nitric oxide electrochemical sensor
(1) Adding lithium iron phosphate, conductive carbon black and polyvinylidene fluoride into N-methylpyrrolidone according to a mass ratio of the lithium iron phosphate to the conductive carbon black to the polyvinylidene fluoride of 8;
(2) Performing charge-discharge circulation on the CR250 type button battery obtained in the step (1), specifically discharging and then charging under the conditions that the voltage range is 1.8-4.2V, the current is 0.3C and the temperature is 25 ℃, discharging to 1.8V to be in a final state after 3 times of charge-discharge circulation, disassembling the CR250 type button battery, taking out an anode, cleaning the anode by absolute ethyl alcohol, drying for 4 hours at 60 ℃, and scraping a lithium-rich lithium iron phosphate material on the anode;
(3) Dispersing the lithium-rich lithium iron phosphate material prepared in the step (2) into deionized water according to the proportioning concentration of 3.3mg/mL to obtain an electrode modification solution, and dropwise adding 5 mu L of the electrode modification solution to an area of 0.07cm 2 Drying the screen-printed electrode at 50 ℃ for 30min to prepare a working electrode coated with a lithium-rich lithium iron phosphate material;
(4) And (3) assembling the working electrode coated with the cobalt pyrophosphate nanomaterial on the surface, which is prepared in the step (3), together with an electrochemical workstation, a counter electrode (screen-printed carbon electrode), a reference electrode (screen-printed carbon electrode), an electrolytic cell and an electrolyte (phosphate buffer solution with the concentration of 0.01mol/L and the pH = 7.4) into the nitric oxide electrochemical sensor.
Example 2
Preparing lithium-rich lithium iron phosphate material, coating working electrode of the material and constructing nitric oxide electrochemical sensor
(1) Adding lithium iron phosphate, conductive carbon black and polyvinylidene fluoride into N-methylpyrrolidone according to a mass ratio of the lithium iron phosphate to the conductive carbon black to the polyvinylidene fluoride of 4;
(2) Performing charge-discharge circulation on the CR250 type button battery obtained in the step (1), specifically, discharging and then charging under the conditions that the voltage range is 2.0-3.9V, the current is 0.1C and the temperature is 23 ℃, discharging for 3 times and discharging to 2.0V to be a final state, disassembling the CR250 type button battery and taking out an anode, cleaning the anode by absolute ethyl alcohol, drying for 5 hours at 20 ℃, and scraping the lithium-rich lithium iron phosphate material on the anode;
(3) Mixing the lithium-rich lithium iron phosphate material prepared in the step (2) withDispersing 3.8mg/mL of the mixture in deionized water to obtain an electrode modification solution, and dripping 5 mu L of the electrode modification solution to an area of 0.07cm 2 Drying the screen-printed electrode at 20 ℃ for 60min to prepare a working electrode coated with a lithium-rich lithium iron phosphate material;
(4) And (3) assembling the working electrode coated with the cobalt pyrophosphate nanomaterial on the surface, which is prepared in the step (3), together with an electrochemical workstation, a counter electrode (screen printing carbon electrode), a reference electrode (screen printing Ag/AgCl electrode), an electrolytic cell and an electrolyte (phosphate buffer solution with the concentration of 0.1mol/L and the pH = 7.2) into the nitric oxide electrochemical sensor.
Example 3
Preparing lithium-rich lithium iron phosphate material, coating working electrode of the material and constructing nitric oxide electrochemical sensor
(1) Adding lithium iron phosphate, conductive carbon black and polyvinylidene fluoride into N-methylpyrrolidone according to the mass ratio of the lithium iron phosphate to the conductive carbon black to the polyvinylidene fluoride of 9.5, uniformly mixing to obtain a mixture, coating the mixture on an aluminum foil with the thickness of 160 mu M, drying at 110 ℃ for 11 hours to obtain an aluminum foil loaded with the lithium iron phosphate, taking the aluminum foil loaded with the lithium iron phosphate as a positive electrode, a metal lithium sheet as a counter electrode, a polyethylene microporous membrane as a diaphragm, and taking a lithium hexafluorophosphate electrolyte with the concentration of 1M of lithium hexafluorophosphate as an electrolyte, and assembling into a CR250 type button battery in a glove box filled with argon;
(2) Performing charge-discharge circulation on the CR250 type button battery obtained in the step (1), specifically discharging and then charging under the conditions that the voltage range is 2.2-4.5V, the current is 0.5C and the temperature is 27 ℃, discharging to 2.2V after 3 times of charge-discharge circulation to be a final state, disassembling the CR250 type button battery and taking out an anode, cleaning the anode by absolute ethyl alcohol, drying for 2 hours at 80 ℃, and scraping a lithium-rich lithium iron phosphate material on the anode;
(3) Dispersing the lithium-rich lithium iron phosphate material prepared in the step (2) into deionized water according to the proportioning concentration of 2.8mg/mL to obtain an electrode modification solution, and dropwise adding 10 mu L of the electrode modification solution to the area of 0.1cm 2 Drying at 100 deg.C for 20min to obtain a coatingA working electrode comprising a lithium-rich lithium iron phosphate material;
(4) And (3) assembling the working electrode coated with the cobalt pyrophosphate nanomaterial on the surface, which is prepared in the step (3), together with an electrochemical workstation, a counter electrode (screen printing carbon electrode), an electrolytic cell and an electrolyte (phosphate buffer solution with the concentration of 0.05mol/L and the pH = 7.0) into the nitric oxide electrochemical sensor.
Fig. 1 is a scanning electron microscope image and a perspective electron microscope image of the lithium-rich lithium iron phosphate material prepared in example 1, wherein a in fig. 1 is a scanning electron microscope image, and b in fig. 1 is a transmission electron microscope image, and as can be seen from fig. 1, the lithium-rich lithium iron phosphate material is micro-nano-sized and has a good lattice structure.
Fig. 2 is an X-ray diffraction pattern of the lithium-rich lithium iron phosphate material prepared in example 1, and it can be seen from fig. 2 that the lithium-rich lithium iron phosphate material has a better lattice structure of the lithium iron phosphate material.
Fig. 3 is a scanning electron microscope image and a perspective electron microscope image of the lithium-rich lithium iron phosphate material prepared in example 2, where a in fig. 3 is a scanning electron microscope image, and b in fig. 3 is a transmission electron microscope image, and as can be seen from fig. 3, the lithium-rich lithium iron phosphate material is micro-nano-sized and has a good lattice structure.
Fig. 4 is an X-ray diffraction pattern of the lithium-rich lithium iron phosphate material prepared in example 2, and it can be seen from fig. 4 that the lithium-rich lithium iron phosphate material has a better lattice structure of the lithium iron phosphate material.
Fig. 5 is a scanning electron microscope image and a perspective electron microscope image of the lithium-rich lithium iron phosphate material prepared in embodiment 3, where a in fig. 5 is a scanning electron microscope image, and b in fig. 5 is a transmission electron microscope image, and as can be seen from fig. 5, the lithium-rich lithium iron phosphate material has a micro-nano level size and a good lattice structure.
Fig. 6 is an X-ray diffraction pattern of the lithium-rich lithium iron phosphate material prepared in example 3, and it can be seen from fig. 6 that the lithium-rich lithium iron phosphate material has a better lattice structure of the lithium iron phosphate material.
Example 4
Taking the lithium iron phosphate material discharged to different voltages in example 1, measuring the lithium ion content of different lithium iron phosphate materials by using an inductively coupled plasma mass spectrometry, and comparing the lithium ion content of different lithium iron phosphate materials, the result is shown in fig. 7, and as can be seen from fig. 7, the lithium ion content of the lithium iron phosphate material discharged to the lowest voltage is higher than a theoretical value (4.4%, w/w), which proves that the material is a lithium-rich lithium iron phosphate material.
Example 5
A certain amount of NO solution was added to the electrolyte of the sensor constructed in example 1, and the cyclic voltammetric response of the sensor to NO was tested at a voltage range of-0.2-1.1V, while the cyclic voltammetric response of the sensor to phosphate buffer solution was used as a blank. As shown in fig. 8, it can be seen from fig. 8 that the sensor constructed in example 1 showed NO oxidation peak at 0.85V, indicating that the sensor has a significant electrochemical catalytic oxidation capability for NO.
Example 6
Testing the timing current response of the sensor constructed in the embodiment 1 to NO under the peak voltage (0.85V) of a cyclic voltammetry curve, continuously adding NO solutions with different concentrations into the electrolyte of the sensor constructed in the embodiment 1 during testing, wherein the time interval is 50s, recording the relation curve of response time and current value, and obtaining the ampere-fold response diagram of the sensor to NO, wherein the result is shown in FIG. 9, the upper right small graph in the diagram is the influence time diagram of the sensor to NO, and as can be known from FIG. 9, after the NO with different concentrations is added, the current response of the sensor is continuously increased and reaches a steady state within a relatively fast time, and the response time is less than 2s; the relationship between NO concentration and current response is plotted in FIG. 9, and as shown in FIG. 10, it can be seen from FIG. 10 that the current response of the sensor is 5X 10 in the case of NO concentration -10 -2.9×10 -7 Shows good linear relation in the mol/L range, and the detection limit is 1.2 multiplied by 10 -10 mol/L。
Example 7
Solutions of different substances are sequentially added into the electrolyte of the sensor constructed in the embodiment 1, the timing current response of the sensor to different interference components is tested, the test voltage is 0.85V, the time interval for adding different interferents is 50s, an ampere response curve of the sensor to the selectivity test of different interference components is obtained, and the result is shown in fig. 11, and as can be seen from fig. 11, the sensor has good selectivity to NO.
Example 8
The NO solution is added into the electrolytic cell of the sensor constructed in the embodiment 1, the cyclic voltammetry response of the sensor placed for different days to NO is tested under the voltage range of-0.2-1.1V, the same electrochemical sensor is used in the test, the test is carried out once every 5 days, the concentration of NO added every time is kept unchanged, the test is carried out for 7 times, and a stability test result graph stored for 30 days is obtained, the result is shown in figure 12, and as can be seen from figure 12, the sensor has good test stability.
Example 9
Cells are inoculated on the surface of the working electrode coated with the lithium-rich lithium iron phosphate material prepared in the embodiment 1, the electrode for in-situ cell growth is obtained after the cells are cultured in a cell culture box for 12 hours, the electrode is assembled in the sensor constructed in the embodiment 1, and the timing current response of NO release of the cells under the stimulation of acetylcholine drug is tested, so that the current response of the sensor for in-situ detection of NO released by the cells growing on the electrode is obtained. In a comparative experiment, the cell of the sensor constructed in example 1 was replaced with a petri dish in which cells were grown, and the electrolyte was still a phosphate buffer solution with a concentration of 0.01mol/L and pH =7.4, and the current response of cells in the petri dish to release NO was obtained by measuring the timed current response of cells to release NO under the stimulation of acetylcholine drug. As shown in FIG. 13, it is understood from FIG. 13 that NO released from the cells directly grown on the working electrode in the sensor can be detected more efficiently.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (7)
1. The application of the electrochemical sensor in NO detection is characterized in that the electrochemical sensor comprises an electrochemical workstation, a working electrode, a counter electrode, a reference electrode, an electrolytic cell and electrolyte, wherein the surface of the working electrode is coated with a lithium-rich lithium iron phosphate material;
the preparation method of the lithium-rich lithium iron phosphate material comprises the following steps: (1) Adding lithium iron phosphate, conductive carbon black and polyvinylidene fluoride into N-methyl pyrrolidone, uniformly mixing to obtain a mixture, coating the mixture on an aluminum foil and drying to obtain an aluminum foil loaded with the lithium iron phosphate, taking the aluminum foil loaded with the lithium iron phosphate as a positive electrode, a metal lithium sheet as a counter electrode, a polyethylene microporous membrane as a diaphragm and a lithium hexafluorophosphate electrolyte as an electrolyte, and assembling to obtain the button battery;
(2) And (2) performing charge-discharge circulation on the button battery obtained in the step (1), then disassembling the button battery, taking out the positive electrode, cleaning and drying the positive electrode, and scraping the lithium-rich lithium iron phosphate material on the positive electrode.
2. The application of claim 1, wherein in the step (1), the mass ratio of the lithium iron phosphate to the conductive carbon black to the polyvinylidene fluoride is 4-9; the thickness of the aluminum foil is 160-180 mu M, the concentration of lithium hexafluorophosphate in the lithium hexafluorophosphate electrolyte is 1M, and the button cell is a CR250 type button cell.
3. The use according to claim 1, wherein in step (1), the drying is carried out for 10-12h at 110-120 ℃.
4. The use according to claim 1, wherein in step (2), the charge-discharge cycle is performed by first discharging and then charging under the conditions of a voltage ranging from 2.0 ± 0.2V to 4.2 ± 0.3V, a current ranging from 0.1 to 0.5C, and a temperature ranging from 23 to 27 ℃, and the final state is performed by discharging to the lowest voltage after the cycle.
5. The application of claim 1, wherein in the step (2), the organic solution is used as a cleaning solution during cleaning, and the drying is specifically drying at 20-80 ℃ for 2-5h.
6. The use of claim 1, wherein the working electrode is prepared by: dispersing the lithium-rich lithium iron phosphate material in water according to the proportioning concentration of 2.8-3.8mg/mL to obtain an electrode modification solution, coating the electrode modification solution on an electrode, and drying.
7. Use according to claim 6, wherein the drying is in particular a drying at 20-100 ℃ for 20-60min.
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