CN113745509A - Phosphorus-nitrogen doped biomass hard carbon material and preparation method and application thereof - Google Patents
Phosphorus-nitrogen doped biomass hard carbon material and preparation method and application thereof Download PDFInfo
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- CN113745509A CN113745509A CN202110908449.8A CN202110908449A CN113745509A CN 113745509 A CN113745509 A CN 113745509A CN 202110908449 A CN202110908449 A CN 202110908449A CN 113745509 A CN113745509 A CN 113745509A
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention discloses a phosphorus-nitrogen doped biomass hard carbon material and a preparation method and application thereof. The biomass hard carbon material is derived from tea stems, and the specific method comprises the following steps: step 1) ball-milling or crushing tea stems, sieving, repeatedly soaking and cleaning with ethanol until the tea stems are colorless, then putting the tea stems into a hydrochloric acid solution, heating while stirring, washing with water and drying to obtain a biomass carbon precursor. And 2) transferring the obtained biomass carbon precursor to a tubular furnace, and calcining under the protection of inert gas to obtain the hard carbon material. And 3) dissolving the obtained hard carbon material and nitrogen source in deionized water, stirring, adding a phosphorus source, continuously stirring, filtering and drying. And 4) calcining the material obtained in the step 3 in inert protective gas to obtain the phosphorus-nitrogen doped biomass hard carbon material. The preparation method is low in preparation cost, can be used for mass production, and the obtained material has high conductivity, can be applied to the cathode material of the lithium/sodium/potassium ion battery, and has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of waste biomass material treatment and power technology electrochemical energy storage, and particularly relates to a phosphorus-nitrogen doped biomass hard carbon material and a preparation method and application thereof.
Background
As a high energy density energy storage technology, lithium ion batteries have been widely used in large-scale energy storage systems such as electric vehicles and smart grids. The sodium/potassium element of the same main group with the lithium element has similar chemical properties, abundant reserves, low price and no pollution to the environment, so the sodium/potassium ion battery can be used as beneficial supplement of large-scale energy storage of the lithium ion battery.
The hard carbon is a carbonaceous material which is difficult to graphitize, has uneven pore distribution and larger specific surface area, has the advantages of larger carbon layer spacing and the like, is very suitable for the intercalation/deintercalation of lithium/sodium/potassium ions, and is a very promising anode material of an alkali metal ion battery. As a hard carbon material, the biomass carbon is mainly amorphous carbon consisting of small graphitized fragments distributed randomly and a hierarchical pore structure, has good geometric shape, hierarchical structure, conductivity, stability, safety and high crystallinity, and is widely used for research on alkali metal ion battery cathode materials. However, the cycle performance of the hard carbon material obtained by carbonizing the general biomass material is not ideal enough, and the first coulombic efficiency is low.
Meanwhile, a plurality of literature reports exist for preparing hard carbon from biomass carbon sources such as pine nut shells, peanut shells, mangosteen shells, shaddock peels, coconut shells and the like. In China in the country of tea trees, the planting area of the tea trees is wide, and the tea stalks left after tea leaves are picked every year are numerous and only serve as primary fuel and are hardly reasonably utilized. Compared with other biomass carbon sources, such as peanut shell shaddock peel and the like, tea stalks are inoculated by soil, photosynthesis is needed, and a small amount of chlorophyll and mineral substances are contained, so that impurities exist in the prepared hard carbon, and the carbon content is low. Therefore, the tea stalks which are used as wastes are used as a carbon source to prepare the hard carbon material, so that the method has good economic benefit and market prospect.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides the phosphorus-nitrogen doped biomass hard carbon material, and the preparation method and the application thereof, and solves the problems of treatment and reutilization of waste tea stems, unsatisfactory performance of the biomass hard carbon material and the like in the background art.
The technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the phosphorus-nitrogen doped biomass hard carbon material is provided, the tea stalk is used as a biomass carbon source, and the method comprises the following steps:
step 1: crushing tea stems by a mechanical method, sieving by a 50-200 mesh sieve, repeatedly soaking and cleaning with ethanol until the tea stems are colorless, then putting the tea stems into a hydrochloric acid solution, heating while stirring, wherein the heating temperature is 90-120 ℃, and the stirring time is 1-4 h; washing and drying to obtain a biomass carbon precursor;
step 2: calcining the obtained biomass carbon precursor under the protection of inert gas, wherein the temperature of the calcination is firstly raised to 100-class temperature of 150 ℃ for 1-2h, the temperature is continuously raised to 500-class temperature of 600 ℃ for 1-2h, and finally the temperature is raised to 900-class temperature of 1300 ℃ for 1-6h, and the heating rate is 5-10 ℃/min, so as to obtain a hard carbon material;
and step 3: dissolving the obtained hard carbon material and nitrogen source in deionized water, stirring, adding a phosphorus source, continuously stirring, filtering and drying; wherein the mass ratio of the hard carbon material to the nitrogen source to the phosphorus source is 1: 2-5: 10-30 parts of;
and 4, step 4: and (3) calcining the material obtained in the step (3) in inert gas, heating the calcined material to 500-700 ℃ at the heating rate of 5-10 ℃/min, and keeping the temperature for 2-4h to obtain the phosphorus-nitrogen doped biomass hard carbon material.
In a preferred embodiment of the present invention, in step 3, the nitrogen source is at least one of melamine or urea.
In a preferred embodiment of the present invention, in step 3, the phosphorus source is at least one of phytic acid or sodium hypophosphite.
In a preferred embodiment of the present invention, the inert gas is at least one of nitrogen or argon.
In a preferred embodiment of the present invention, in step 3, the stirring time for dissolving the hard carbon material and the nitrogen source in the deionized water is 2 to 24 hours, and the stirring time for adding the phosphorus source is 1 to 6 hours.
The invention also provides a phosphorus-nitrogen doped biomass hard carbon material prepared by the method.
In a preferred embodiment of the present invention, the tunnel structure has an ordered porous tunnel structure, and graphitized fragments are attached to the side wall and the surface of the tunnel, and the graphitized fragments have a size of 100-500nm and are formed by covalently bonding nitrogen, phosphorus and carbon elements. Disordered lattice stripe-shaped hard carbon with carbon content more than or equal to 95 percent, and the carbon layer spacing is not less than 0.380 nm.
The invention also provides a battery, and the negative electrode material of the battery is the phosphorus-nitrogen doped biomass hard carbon material.
The invention also provides a tea stem recycling method, which is characterized by comprising the following steps: the waste tea stalks are used as a biomass carbon source, the biomass hard carbon material is prepared by the method, and then:
and 5: and (3) assembling the lithium ion battery, the sodium ion battery or the potassium ion battery by using the obtained phosphorus-nitrogen doped biomass hard carbon material as a battery negative electrode material.
Compared with the background technology, the technical scheme has the following advantages:
1. the invention recycles the tea stalk waste, has low cost and simple operation, and is beneficial to mass production with low cost;
2. according to the invention, the precursor is prepared by acid washing treatment at a specific temperature, and the sequence, proportion and stirring time of the added nitrogen source and phosphorus source are controlled, so that the doping concentration of nitrogen and phosphorus and the dispersibility of the material are controlled, the problems of chlorophyll and mineral impurities and the like of tea stalks as biomass carbon sources are solved, the carbon content of the biomass hard carbon material after carbonization is high (more than or equal to 95 wt%), and the biomass hard carbon material has higher specific capacity, good conductivity, small polarization, high first coulomb efficiency and good cycle performance as a battery cathode material.
Drawings
FIG. 1 is a scanning electron microscope image of a biomass carbon material obtained in example 1 of the present invention.
FIG. 2 is a transmission electron microscope image of biomass carbon material obtained in example 1 of the present invention at different magnifications; left-50 nm and right-5 nm.
FIG. 3 is a mapping analysis chart of a biomass carbon material obtained in example 1 of the present invention.
Fig. 4 is XRD (left) and Raman (right) patterns of biomass carbon materials obtained in example 1 and comparative example 1 of the present invention.
FIG. 5 is a graph showing cycle characteristics of biomass carbon materials obtained in example 1 and comparative example 1 of the present invention.
Fig. 6 is a graph showing electrochemical rate performance of biomass carbon materials obtained in example 1 and comparative example 1 of the present invention.
Detailed Description
Example 1
The preparation method of the phosphorus-nitrogen doped biomass hard carbon material comprises the following steps:
step 1: crushing tea stems by a mechanical method, sieving by a 100-mesh sieve, repeatedly soaking and cleaning by ethanol until the tea stems are colorless, then putting the tea stems into a 1M hydrochloric acid solution, heating to 120 ℃, stirring for 1h, washing with water and drying to obtain a biomass carbon precursor;
step 2: transferring the obtained biomass carbon precursor into a tubular furnace, calcining under the protection of argon gas, wherein the calcining procedure is to heat up to 150 ℃, keep for 2h, heat up to 600 ℃ from 150 ℃, keep for 2h, heat up to 1100 ℃ from 600 ℃, keep for 3h, naturally cool to room temperature to obtain a hard carbon material, and the heating rates are both 5 ℃/min to obtain the hard carbon material;
and step 3: adding 240mg of carbonized hard carbon material into 240mL of deionized water in a flat-bottomed flask, adding 600mg of melamine, stirring for 24 hours at 900r/min, adding 7.2g of phytic acid, continuing stirring for 6 hours, filtering and drying;
and 4, step 4: and (4) transferring the material obtained in the step (3) into a tubular furnace, heating to 700 ℃ at a heating rate of 5 ℃/min under an argon atmosphere, keeping the temperature for 2 hours, and naturally cooling to room temperature to obtain the phosphorus-nitrogen doped biomass hard carbon material.
Please refer to fig. 1, which is a scanning electron microscope image of the biomass carbon material prepared in this example: the scanning electron microscope image can show that the nano-porous material has an ordered porous tunnel structure, and smaller particles are attached to the surface of the nano-porous material. In FIG. 2, the multilayer structure inside can be seen from the transmission electron microscope picture, the lattice stripes of the hard carbon disorder can be seen from the high resolution picture, and the carbon layer spacing is 0.44 nm. In the mapping analysis chart of the biomass carbon material in fig. 3, the element distribution of nitrogen, phosphorus and carbon can be seen, and the phosphorus and nitrogen elements can be seen to be uniformly distributed in the whole carbon material.
The embodiment also provides a button cell made of the negative electrode material of the sodium-ion battery. The biomass hard carbon material prepared in the embodiment is used as a sodium ion battery cathode material for button cell characterization: 280mA g-1The current is circulated for 100 times (28mA g)-1Current activation for 2 cycles) and rate testing at different current densities.
Comparative example 1
Comparative example 1 differs from example 1 in that: and (3) preparing the biological hard carbon material which is not doped with the phosphorus and nitrogen element without the phosphorus and nitrogen doping step in the step (3).
Please refer to fig. 4 XRD and Raman plots of biomass carbon material obtained in example 1 and comparative example 1: it can be seen that the sample of comparative example 1 shows two broad and dispersed peaks at 22 ° (002) and 42 ° (100), indicating that the sample is amorphous hard carbon of a disordered structure. The diffraction peak of the (002) crystal plane of the material of example 1 gradually shifted to a low angle with the doping of phosphorus and nitrogen, indicating that the interlayer spacing significantly increased, which is attributed to the introduction of heteroatoms. The interlayer distances of the materials of example 1 and comparative example 1, calculated by bragg formula, were 0.394 and 0.370, respectively, greater than the interlayer spacing of the in-plane graphite, which is a necessary condition for improving ion kinetics. Both samples in the raman spectrum showed a broad disorder-induced D band and an in-plane vibrational G band. The integrated intensity of the D/G peak may reflect the degree of graphitization of the carbon. Two typical peaks at 1347cm were observed in the Raman spectrum of the sample-1And 1582cm-1In example 1, the half-width of the D peak is larger, and the peak position is slightly shifted to the low wave number direction, thus indirectly proving the existence of nitrogen and phosphorus doping. According to calculation, example 1 and comparative exampleThe integrated intensity ratios of the D/G peaks of 1 were 1.98 and 1.73, respectively, which indicates that nitrogen-phosphorus doping can promote the amorphous structure of the carbon material, which is consistent with XRD results.
And (3) taking the biomass hard carbon material prepared in the comparative example 1 as a negative electrode material of the sodium-ion battery to perform button cell characterization: 280mA g-1The current is circulated for 100 times (28mA g)-1Current activation for 2 cycles) and rate testing at different current densities.
Referring to fig. 5 and 6, there are shown a graph comparing the cycle performance and a graph comparing the electrochemical rate performance of biomass carbon materials obtained in example 1 and comparative example 1, respectively: the figure shows that the phosphorus-nitrogen doped biomass carbon material of example 1 has excellent electrochemical rate capability and cycle performance at 28mAg compared with the material of comparative example 1-1The first charge-discharge coulombic efficiency under the current density is 89%, and the first charge-discharge coulombic efficiency is 280mA g-1The current density of the battery is 100 cycles, and the initial charging specific capacity is 280mAh g-1The specific charging capacity after 100 cycles is 262mAh g-1The capacity retention rate is 93.5%, the cycle stability is very good, the high current also keeps very good stability in the multiplying power test, and the high current is recovered to 28mA g-1And the material can still stably circulate, so the material has good application prospect.
Comparative example 2
Common biomass carbon materials are commercially available.
The common biomass hard carbon material pole piece has low compaction density, low first-time efficiency which can reach about 80 percent at most, and poor effect in the practical application of negative electrode materials. For example, biomass pitch at 28mA g-1The reversible capacity of the current density of the capacitor can only reach 120mAh g-1The reversible capacity of (a). While example 1, as a hard carbon material, possessed 316mAh g at the same current density-1The first coulombic rate of the high reversible capacity can reach 89 percent.
Comparative example 3
The common nitrogen-phosphorus-doped carbon fiber material purchased in the market is 56mA g-1Can provide about 290mAh g under the current density-1But the coulombic efficiency is only 64%.
Comparative example 4
Comparative example 4 differs from example 1 in that: the biomass carbon source is corn and platycodon grandiflorum.
The specific capacity is 202mAh g after 100 cycles of circulation under 1C-1In contrast, example 1 had 280mAh g after 100 cycles at 1C-1High reversible capacity of even at 5A g-1About 110mAh g still exists after 3000 cycles of high current density-1The reversible capacity of (a).
Comparative example 5
The tea stalks are treated by adopting the traditional process of activation and carbonization again to obtain the hard carbon material.
Because the specific surface of the tea stem is not high, the hard carbon material obtained by adopting the traditional carbonization process has high specific surface but low capacity and efficiency, and the specific surface is 100mA g-1Current density of 190mAh g only-1The first coulombic efficiency is only 61.4%.
Example 2
Example 2 differs from example 1 in that: the heating temperature of the hydrochloric acid solution in the step 1 is 90 ℃, and the stirring time is 4 h.
Example 3
Example 3 differs from example 1 in that: and (3) heating the temperature of 600 ℃ in the step 2 to 1300 ℃, and keeping the temperature for 1 h.
Example 4
Example 4 differs from example 1 in that: and (3) heating the temperature of 600 ℃ in the step 2 to 900 ℃, and keeping the temperature for 6 hours.
Example 5
Example 5 differs from example 1 in that: the inert protective gas in the step 2 and the step 3 is nitrogen.
Example 6
Example 6 differs from example 1 in that: in the step 3, the mass ratio of the hard carbon material to the nitrogen source to the phosphorus source is 1: 2: 10.
example 7
Example 7 differs from example 1 in that: in step 3, the nitrogen source is urea.
Example 8
Example 8 differs from example 1 in that: in step 3, the phosphorus source is sodium hypophosphite.
Example 9
Example 9 differs from example 1 in that: and 3, dissolving the hard carbon material and the nitrogen source in the deionized water for 2 hours under stirring, and adding the phosphorus source for 1 hour under stirring.
Example 10
Example 10 differs from example 1 in that: the calcination mode in the step 3 is constant temperature of 500 ℃ for 4 hours.
Example 11
Example 11 differs from example 1 in that: and 4, taking the target product as a lithium ion battery cathode material to perform button cell characterization.
Example 12
Example 12 differs from example 1 in that: and 4, taking the target product as a negative electrode material of the potassium ion battery to perform button battery characterization.
The phosphorus-nitrogen doped biomass hard carbon material prepared in the example is subjected to related physical and chemical performance tests, and the results are as follows:
TABLE 1 Table of physical Property parameters of the materials obtained in the examples
As can be seen from Table 1, the preparation method solves the problem that the carbon content of the material prepared by using tea stalks as a biomass carbon source is not ideal, so that the carbon content of the hard biomass carbon material after carbonization is high (more than or equal to 95 wt%); meanwhile, the carbon layer spacing materials obtained in the embodiments can adapt to the deintercalation of the alkali metal batteries with different ionic radius sizes.
TABLE 2 electrochemical performance data sheet of the examples
As can be seen from Table 2, the phosphorus-nitrogen doped biomass hard carbon material prepared by the method has the advantages of high specific capacity, good conductivity, small polarization, high coulombic efficiency for the first time, good cycle performance, capability of being applied to various alkali metal battery cathode materials, and good application prospect.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; while the present invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a phosphorus-nitrogen doped biomass hard carbon material is characterized by comprising the following steps: the method takes tea stalks as a biomass carbon source and comprises the following steps:
step 1: crushing tea stems by a mechanical method, sieving by a 50-200 mesh sieve, repeatedly soaking and cleaning with ethanol until the tea stems are colorless, then putting the tea stems into a hydrochloric acid solution, heating while stirring, wherein the heating temperature is 90-120 ℃, and the stirring time is 1-4 h; washing and drying to obtain a biomass carbon precursor;
step 2: calcining the obtained biomass carbon precursor under the protection of inert gas, heating to 100-;
and step 3: dissolving the obtained hard carbon material and nitrogen source in deionized water, stirring, adding a phosphorus source, continuously stirring, filtering and drying; wherein the mass ratio of the hard carbon material to the nitrogen source to the phosphorus source is 1: 2-5: 10-30 parts of;
and 4, step 4: and (3) calcining the material obtained in the step (3) in inert gas, heating the calcined material to 500-700 ℃ at the heating rate of 5-10 ℃/min, and keeping the temperature for 2-4h to obtain the phosphorus-nitrogen doped biomass hard carbon material.
2. The method for preparing a phosphorus-nitrogen doped biomass hard carbon material according to claim 1, wherein the method comprises the following steps: in step 3, the nitrogen source is at least one of melamine or urea.
3. The method for preparing a phosphorus-nitrogen doped biomass hard carbon material according to claim 1, wherein the method comprises the following steps: in the step 3, the phosphorus source is at least one of phytic acid or sodium hypophosphite.
4. The method for preparing a phosphorus-nitrogen doped biomass hard carbon material according to claim 1, wherein the method comprises the following steps: the inert gas is at least one of nitrogen or argon.
5. The method for preparing a phosphorus-nitrogen doped biomass hard carbon material according to claim 1, wherein the method comprises the following steps: in the step 3, the stirring time for dissolving the hard carbon material and the nitrogen source in the deionized water is 2-24h, and the stirring time for adding the phosphorus source is 1-6 h.
6. A phosphorus-nitrogen doped biomass hard carbon material is characterized in that: prepared by the method of any one of claims 1 to 5.
7. The phosphorus-nitrogen doped biomass hard carbon material as claimed in claim 6, wherein: the graphite-carbon composite material has an ordered porous tunnel structure, graphitized fragments are attached to the side wall and the surface of the tunnel, the size of the graphitized fragments is 100-500nm, and the graphitized fragments are formed by combining nitrogen and phosphorus elements with carbon elements through covalent bonds.
8. The phosphorus-nitrogen doped biomass hard carbon material as claimed in claim 6, wherein: disordered lattice stripe-shaped hard carbon with carbon content more than or equal to 95 percent, and the carbon layer spacing is not less than 0.380 nm.
9. A battery, characterized by: the battery negative electrode material is the phosphorus-nitrogen-doped biological hard carbon material as defined in any one of claims 6 to 8.
10. A method for recycling tea stems is characterized by comprising the following steps: the method for preparing the biomass hard carbon material by using the waste tea stalks as a biomass carbon source according to any one of claims 1 to 5, further comprising:
and 5: and (3) assembling the lithium ion battery, the sodium ion battery or the potassium ion battery by using the obtained phosphorus-nitrogen doped biomass hard carbon material as a battery negative electrode material.
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| CN116924389A (en) * | 2023-08-30 | 2023-10-24 | 北京航空航天大学 | Hard carbon, preparation method thereof and sodium ion battery prepared from hard carbon |
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