CN117699752A - Nano red phosphorus-porous carbon composite material and preparation method and application thereof - Google Patents
Nano red phosphorus-porous carbon composite material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 99
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 133
- 239000011259 mixed solution Substances 0.000 claims abstract description 63
- 239000002245 particle Substances 0.000 claims abstract description 43
- 239000000243 solution Substances 0.000 claims abstract description 39
- 241000195649 Chlorella <Chlorellales> Species 0.000 claims abstract description 38
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003929 acidic solution Substances 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 23
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 15
- 238000003763 carbonization Methods 0.000 claims description 13
- 239000011159 matrix material Substances 0.000 claims description 12
- 239000007773 negative electrode material Substances 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000006188 syrup Substances 0.000 claims description 3
- 235000020357 syrup Nutrition 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 31
- 239000011148 porous material Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 229910052698 phosphorus Inorganic materials 0.000 description 14
- 239000011574 phosphorus Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- -1 phosphorus ions Chemical class 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 6
- 238000000643 oven drying Methods 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
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- 230000002829 reductive effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
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- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
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- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
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- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a nano red phosphorus-porous carbon composite material, a preparation method and application thereof. The preparation method comprises the following steps: mixing a pore-forming agent, a solvent, an ethylenediamine solution and red phosphorus to obtain a first mixed solution, mixing chlorella with the first mixed solution, adding the first mixed solution into a first acidic solution, and separating to obtain a first product, wherein the solvent is selected from water and/or a hydrophilic solvent; carbonizing the first product under the condition of protective gas to obtain a second product; and mixing the second product with a second acidic solution, adding a second mixed solution, wherein the second mixed solution is a mixed solution of ethylenediamine solution and red phosphorus, and separating to obtain the nano red phosphorus-porous carbon composite material. The preparation method improves the deposition amount and the dispersion uniformity of the nano red phosphorus particles, remarkably reduces the problem that red phosphorus is converted into white phosphorus in the preparation process, improves the production efficiency and the safety, reduces the cost and is beneficial to realizing large-scale production.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a nano red phosphorus-porous carbon composite material and a preparation method and application thereof.
Background
Phosphorus has high theoretical specific capacity (2596 mAh/g) and safe operating voltage (-0.45V), and has high electrochemical activity in both lithium ion batteries and sodium ion batteries. The phosphorus has a plurality of allotropes of red phosphorus, white phosphorus, black phosphorus, purple phosphorus and the like, wherein the red phosphorus has the advantages of rich content, low market cost, small environmental pollution and the like, and compared with the white phosphorus, the black phosphorus and the purple phosphorus, the red phosphorus has better chemical stability at room temperature and can be suitable for phosphorus-based anode materials in lithium ion batteries and sodium ion batteries. However, red phosphorus has three problems: (1) Has electronic insulation (conductivity is only 10S/cm-14S/cm); (2) Volume changes are large (above 490%) during cycling; (3) commercial red phosphorus is too large in particle size. These problems make red phosphorus as a negative electrode material poor in electrical conductivity and the particles are easily crushed during long cycles, resulting in failure to achieve optimal energy storage.
Aiming at the problems, the traditional technology generally adopts an evaporation condensation method to compound nano-sized red phosphorus with a carbon matrix, and can improve the conductivity and the structural stability in the circulation process, but on one hand, partial white phosphorus is incompletely generated due to conversion in the evaporation condensation method, so that the capacity loss of a composite material can be caused, and the problems of low yield, safety and the like exist, so that the method cannot be applied to mass production; on the other hand, the conventional carbon matrix mainly includes graphene, carbon nanotubes, microporous carbon made of metal-organic frameworks, etc., but these carbon matrices have high cost and are not conducive to mass production.
Disclosure of Invention
Based on the above, it is necessary to provide a nano red phosphorus-porous carbon composite material, a preparation method and application thereof; the preparation method ensures that the nano red phosphorus particles are fully deposited on the bio-based porous carbon, not only improves the deposition amount and dispersion uniformity of the nano red phosphorus particles and effectively inhibits the agglomeration of the nano red phosphorus particles, but also obviously reduces the problem that the nano red phosphorus is converted into white phosphorus in the preparation process, improves the production efficiency and the safety, simultaneously reduces the cost and is beneficial to realizing large-scale production.
A preparation method of a nano red phosphorus-porous carbon composite material comprises the following steps:
mixing a pore-forming agent, a solvent, an ethylenediamine solution and red phosphorus to obtain a first mixed solution, mixing chlorella with the first mixed solution, adding the first mixed solution into a first acidic solution, and separating to obtain a first product, wherein the solvent is selected from water and/or a hydrophilic solvent;
carbonizing the first product under the condition of protective gas to obtain a second product;
and mixing the second product with a second acidic solution, adding a second mixed solution, wherein the second mixed solution is a mixed solution of ethylenediamine solution and red phosphorus, and separating to obtain the nano red phosphorus-porous carbon composite material.
In one embodiment, the step of preparing the first product satisfies at least one of the following conditions:
(1) The mass ratio of the chlorella to the pore-forming agent to the hydrophilic solvent is 2 (4-15) (1-3);
(2) In the first mixed solution, the mass fraction of the red phosphorus is 2% -8%;
(3) In the first mixed solution, the mass fraction of the ethylenediamine solution is 6% -40%;
(4) The first acidic solution is added in a mode selected from the group consisting of batch addition;
(5) The pore-forming agent is at least one selected from sodium carbonate, potassium carbonate, zinc chloride, potassium acetate, sodium bicarbonate, potassium hydroxide, sodium hydroxide, calcium carbonate and calcium chloride;
(6) The hydrophilic solvent is at least one selected from sodium chloride solution, glucose syrup and ethanol.
In one embodiment, the pH of the first acidic solution and the second acidic solution are each independently selected from 1.3-1.6.
In one embodiment, the first acidic solution and the second acidic solution are each independently selected from the group consisting of a dilute hydrochloric acid-containing ethanol solution in which the volume ratio of ethanol to dilute hydrochloric acid is 1 (0.5-30);
and/or the concentration of the dilute hydrochloric acid is 0.025mol/L-0.1mol/L.
In one embodiment, the step of mixing the second product with a second acidic solution and adding the second mixed solution satisfies at least one of the following conditions:
(1) In the second mixed solution, the concentration of red phosphorus is 4g/L-50g/L;
(2) The second mixed solution is added in a mode selected from the group consisting of batch addition.
In one embodiment, the carbonization is performed at a temperature of 400-1100 ℃ for a time of 0.5-30 hours.
A nano red phosphorus-porous carbon composite material prepared by the preparation method of the nano red phosphorus-porous carbon composite material, wherein the nano red phosphorus-porous carbon composite material comprises a porous carbon matrix and nano red phosphorus particles distributed in the porous carbon matrix.
In one embodiment, the nano red phosphorus-porous carbon composite material meets at least one of the following conditions:
(1) The particle size of the nano red phosphorus-porous carbon composite material is 2-10 mu m;
(2) The particle size of the nano red phosphorus particles is 5nm-10nm;
(3) The deposition amount of the nanometer red phosphorus particles in the nanometer red phosphorus-porous carbon composite material is 38% -45%.
The negative electrode plate comprises a negative electrode current collector and a negative electrode active material layer, wherein the negative electrode active material layer comprises the nano red phosphorus-porous carbon composite material.
A battery comprising a negative electrode tab as described above.
According to the preparation method, under the synergistic effect of the acid precipitation of the nano red phosphorus clusters by the liquid phase phosphorus source and the two-step precipitation, on one hand, the problem that red phosphorus is converted into white phosphorus in the preparation process is remarkably reduced, the size of the nano red phosphorus clusters can be quickly regulated and controlled, the production rate and the yield of red phosphorus are improved, and the safety of red phosphorus synthesis is improved; on the other hand, the porous space of the porous carbon is fully utilized, the deposition amount of the nano red phosphorus particles is improved to about 38% -45%, so that the nano red phosphorus particles are dispersed more uniformly, the agglomeration of the nano red phosphorus particles is effectively limited, a large number of pores can be still kept in the composite material after the nano red phosphorus particles are deposited, a buffer space can be provided for the expansion of the nano red phosphorus particles, the cyclic stability is improved, and meanwhile, the nano red phosphorus particles fully fill the pores on the surface of the porous carbon, so that the pores on the surface of the porous carbon are reduced or closed, the quantity of closed pores is improved, and the sodium storage capacity and a low-voltage platform are improved.
In addition, because chlorella is rich in a large amount of amino acid and protein, the chlorella can form porous carbon doped with nitrogen and phosphorus elements after being carbonized as a biological template, so that the composite material has certain defects, is beneficial to enhancing the surface wettability and catalytic activity of the composite material, and can provide more active sites in the charge and discharge process, thereby further improving the electrochemical performance of the composite material.
Therefore, the nano red phosphorus-porous carbon composite material prepared by the preparation method disclosed by the invention is used as a negative electrode material in a battery, and has high initial charge and discharge efficiency and discharge specific capacity and excellent cycle stability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a schematic flow chart of a preparation method according to an embodiment of the present invention;
FIG. 2 is a schematic cross-sectional view of a nano red phosphorus-porous carbon composite according to an embodiment of the present invention;
FIG. 3 is a graph showing the long cycle profile of the sodium ion battery prepared as the negative electrode material in example 1 at a current density of 0.5A/g for 500 cycles, wherein A is the specific discharge capacity for 500 cycles, and B is the initial charge-discharge efficiency for 500 cycles;
fig. 4 is a long cycle curve of example 1 for a sodium ion battery prepared as a negative electrode material at a current density of 0.2A/g for 200 cycles, where a is the specific discharge capacity for 200 cycles and B is the first charge-discharge efficiency for 200 cycles.
Wherein, 10, porous carbon matrix; 101. a void; 20. nano red phosphorus particles.
Detailed Description
The present invention will be described in more detail below in order to facilitate understanding of the present invention. It should be understood, however, that the invention may be embodied in many different forms and is not limited to the implementations or embodiments described herein. Rather, these embodiments or examples are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments or examples only and is not intended to be limiting of the invention.
Referring to fig. 1, a schematic flow chart of a preparation method of a nano red phosphorus-porous carbon composite material provided by the invention comprises the following steps:
s1, mixing a pore-forming agent, a solvent, an ethylenediamine solution and red phosphorus to obtain a first mixed solution, then mixing chlorella with the first mixed solution, adding a first acidic solution, and separating to obtain a first product, wherein the solvent is selected from water and/or a hydrophilic solvent;
s2, carbonizing the first product under the condition of protective gas to obtain a second product;
s3, mixing the second product with a second acidic solution, adding a second mixed solution, wherein the second mixed solution is a mixed solution of ethylenediamine solution and red phosphorus, and separating to obtain the nano red phosphorus-porous carbon composite material.
It will be appreciated that the red phosphorus is selected from commercial red phosphorus, and the invention is not limited in terms of the choice of commercial red phosphorus in terms of the particular brand, etc.; the ethylenediamine solution is preferably an anhydrous ethylenediamine solution.
In the step S1, red phosphorus is dissolved by using an ethylenediamine solution as a liquid-phase phosphorus source, chlorella is used as a carbon source, and a pore-forming agent and a hydrophilic solvent are matched, on one hand, the pore-forming agent can enter the interior of the chlorella along with water and/or the hydrophilic solvent by utilizing the self hydrophilic characteristic of the chlorella, so that the pore-forming is carried out in the interior of the chlorella in the subsequent carbonization process, and porous carbon with high porosity is formed; on the other hand, as the red phosphorus has high solubility in the ethylenediamine, the red phosphorus mainly exists in the ethylenediamine solution in the form of phosphorus ions and phosphorus free radical ions, and the size of the generated nano red phosphorus clusters can be quickly regulated and controlled by regulating and controlling the concentration of hydrogen ions provided by the first acidic solution, and the production rate and the yield of the red phosphorus are improved, and the safety of the red phosphorus during synthesis is improved.
The synthesis principle of the nano red phosphorus cluster comprises the following steps: in the process of dissolving red phosphorus in ethylenediamine, ethylenediamine generates amino anions through self ionization, the amino anions serve as nucleophiles, the 3d orbitals of red phosphorus molecules are attacked, and P-P bonds are cracked to generate polyphosphoric amine anions, wherein the reaction formula is shown as follows:
H 2 N-CH 2 -CH 2 -NH 2 +P n →(H 2 N-CH 2 -CH 2 -NH 3 + )(H 2 N-CH 2 -CH 2 -NH-P n - )；
p after the reaction of the hydrogen ions with the polyphosphoric amine anions n The ring is closed, and P can be recovered from the mixed solution of red phosphorus and ethylenediamine n Cluster, then P n The clusters aggregate and grow to form nano red phosphorus clusters, and the reaction formula is shown as follows: (H) 2 N-CH 2 -CH 2 -NH 3 + )(H 2 N-CH 2 -CH 2 -NH-P n - )+H + →2(H 2 N-CH 2 -CH 2 -NH 3 + )+P n ↓。
In one embodiment, the mass ratio of the chlorella to the pore-forming agent and the solvent is 2 (4-15): 1-3, more preferably 2 (6-10): 1-3, wherein the pore-forming agent comprises at least one of sodium carbonate, potassium carbonate, zinc chloride, potassium acetate, sodium bicarbonate, potassium hydroxide, sodium hydroxide, calcium carbonate and calcium chloride, more preferably sodium carbonate; the hydrophilic solvent includes at least one of sodium chloride solution, glucose syrup and ethanol, and the water is more preferably deionized water.
In one embodiment, the mass fraction of the red phosphorus in the first mixed solution is 2% -8%.
In one embodiment, in the first mixed solution, the mass fraction of the ethylenediamine solution is 6% -40%.
The ratio of the first mixed solution to the chlorella is regulated, so that the chlorella can form rich and uniform pore structures in the subsequent carbonization process, and meanwhile, the nano red phosphorus particles can reach a certain deposition amount in the porous carbon.
It should be noted that the pore-forming agent, the solvent, the ethylenediamine solution and the red phosphorus may be directly mixed, or the pore-forming agent and the solvent may be mixed first, and then the ethylenediamine solution and the red phosphorus may be added.
In one embodiment, the first acidic solution has a pH of 1.3-1.6, preferably an ethanol solution containing dilute hydrochloric acid, wherein the volume ratio of ethanol to dilute hydrochloric acid is 1 (0.5-30), preferably 1 (10-20), more preferably 1:20; the concentration of the dilute hydrochloric acid is 0.025mol/L to 0.1mol/L, preferably 0.025mol/L to 0.05mol/L, and more preferably 0.05mol/L.
In one embodiment, the first acidic solution is added in a manner selected from the group consisting of batch addition, preferably dropwise addition.
The ratio and the adding mode of the first acid solution are regulated, so that the growth of the nano red phosphorus clusters can be controlled more accurately, and the sizes of the nano red phosphorus clusters can be controlled.
In one embodiment, the chlorella is pretreated before mixing the chlorella with the first mixed solution, which specifically comprises: washing chlorella with deionized water, removing impurities, centrifuging and drying.
In the step S2, on the basis of adding acid to the liquid-phase phosphorus source to precipitate nano red phosphorus clusters, the chlorella loaded with the nano red phosphorus clusters is carbonized, the chlorella is completely decomposed into carbon, and simultaneously, pore formers in the chlorella are decomposed to generate pores and form active sites, so that bio-based porous carbon is formed, the nano red phosphorus clusters are gasified and enter the pores with the active sites, gas-phase phosphorus is deposited from the inside of the porous carbon under the action of physical adsorption or chemical adsorption of a carbon matrix and the like at high temperature, the deposition amount of the nano red phosphorus in the direction extending from the inside of the porous carbon to the surface is distributed in a decreasing trend, the problem that the red phosphorus is converted into white phosphorus in the preparation process can be remarkably reduced, the pore space of the porous carbon can be fully utilized, and a large number of pores can be kept for the expansion of nano red phosphorus particles while the deposition amount of the nano red phosphorus particles is improved, so that the circulation stability is improved.
In addition, nitrogen and phosphorus elements converted from proteins and amino acids of the chlorella are doped in the porous carbon, so that the composite material has certain defects, the surface wettability and the catalytic activity of the composite material are enhanced, more active sites can be provided in the charge and discharge process, and the electrochemical performance of the composite material is further improved.
In one embodiment, the carbonization temperature is 400-1100 ℃ for 0.5-30 h, preferably, the carbonization temperature is 500-1000 ℃ for 2-24 h, more preferably, the carbonization temperature is 700-1000 ℃ for 6-12 h, and by controlling the carbonization temperature and time, the carbonization temperature and time not only can ensure that carbon sources are completely decomposed into carbon, but also pore formers are decomposed to generate pores, thereby forming porous carbon with rich pores, and being beneficial to accurately controlling nano red phosphorus particles to be mainly deposited in the internal pores, thereby effectively reducing the problem of converting red phosphorus into white phosphorus in the preparation process.
In one embodiment, the shielding gas includes, but is not limited to, nitrogen, preferably nitrogen.
Because the pores of the porous carbon are mutually communicated, in the step S3, nano red phosphorus clusters can be further subjected to liquid phase impregnation treatment to be permeated and deposited from the surface of the porous carbon to the inside, the deposition amount of the nano red phosphorus clusters in the extending direction from the surface of the porous carbon is distributed in a decreasing trend in consideration of the occupying effect of the deposited nano red phosphorus clusters, and the pores of the surface of the porous carbon are reduced or closed due to the fact that the nano red phosphorus clusters fully fill the pores of the surface of the porous carbon, so that the quantity of closed pores is improved, and the sodium storage capacity and a low-voltage platform are improved.
Furthermore, under the synergistic effect of acid precipitation of the nano red phosphorus clusters and two-step precipitation of the liquid phase phosphorus source, the pore space of the porous carbon is fully utilized, the precipitation amount of the nano red phosphorus particles is improved to about 38% -45%, the nano red phosphorus particles are dispersed more uniformly, the agglomeration of the nano red phosphorus particles is effectively limited, a large number of pores can be still maintained in the composite material after the nano red phosphorus particles are precipitated, a buffer space can be provided for the expansion of the nano red phosphorus particles, and the composite material has excellent cycle stability while the conductivity of the composite material is improved.
In one embodiment, the second acidic solution has a pH of 1.3-1.6, preferably an ethanol solution containing dilute hydrochloric acid, wherein the volume ratio of ethanol to dilute hydrochloric acid is 1 (0.5-30), preferably 1 (10-20); the concentration of the dilute hydrochloric acid is 0.025mol/L to 0.1mol/L, preferably 0.025mol/L to 0.05mol/L, and more preferably 0.05mol/L.
In one embodiment, the concentration of red phosphorus in the second mixed solution is 4g/L to 50g/L, preferably 5g/L to 15g/L; the ethylenediamine solution in the second mixed solution is preferably an anhydrous ethylenediamine solution.
In one embodiment, the second mixed solution is added in a manner selected from the group consisting of batch addition, preferably dropwise addition, and more preferably, dropwise addition of the second mixed solution while stirring and mixing the second product with the second acidic solution.
The proportion of the second acid solution and the adding mode of the second mixed solution are regulated, so that the growth of the nano red phosphorus clusters can be controlled more accurately, the nano red phosphorus clusters are more uniform in size, the particle size is smaller, and the cyclic stability of the composite material is improved.
The types and proportions of the first acidic solution and the second acidic solution may be the same or different, and the present invention is not limited thereto.
In one embodiment, after the second product is mixed with the second acidic solution and the second mixed solution is added, the mixture is fully stirred, and then the red phosphorus-porous carbon nano-composite material is obtained through separation, washing, drying and other treatments.
Referring to fig. 2, a schematic cross-sectional structure of a nano red phosphorus-porous carbon composite material prepared by the preparation method of the nano red phosphorus-porous carbon composite material according to the present invention is shown, wherein the nano red phosphorus-porous carbon composite material comprises a porous carbon matrix 10 and nano red phosphorus particles 20 distributed in the porous carbon matrix 10.
Specifically, the porous carbon matrix 10 has abundant pores 101, and the nano red phosphorus particles 20 are filled in the pores 101 inside and on the surface of the porous carbon matrix 10.
It should be noted that, most of the pores 101 in the porous carbon substrate 10 have a size larger than the particle size of the nano red phosphorus particles 20, and most of the pores 101 are filled with the nano red phosphorus particles 20, and in order to more fully represent the filling condition of the nano red phosphorus-porous carbon composite material, a part of the pores 101 having a smaller size and the pores 101 not filled with the nano red phosphorus particles 20 are also illustrated in fig. 2, and fig. 2 represents only one cross-sectional structure condition of the nano red phosphorus-porous carbon composite material provided by the present invention, and does not represent all of the nano red phosphorus-porous carbon composite material.
In one embodiment, the particle size of the nano red phosphorus-porous carbon composite material is 2 μm to 10 μm, and the particle size of the nano red phosphorus particles 20 is 5nm to 10nm.
In one embodiment, the nano red phosphorus-porous carbon composite material has a deposition amount of nano red phosphorus particles 20 of 38% -45%.
The nano red phosphorus-porous carbon composite material provided by the invention is used as a negative electrode material in a battery, and has high initial charge and discharge efficiency and discharge specific capacity, and excellent cycle stability.
The invention provides a negative pole piece. The negative electrode plate comprises a negative electrode current collector and a negative electrode active material layer, wherein the negative electrode active material layer comprises the nano red phosphorus-porous carbon composite material. It is understood that the negative electrode active material layer may further include a binder or the like, which is not limited in the present invention.
The invention also provides a battery which can be a lithium ion battery or a sodium ion battery. The battery includes a negative electrode tab as described above. It is understood that the battery further comprises a positive electrode plate, a diaphragm and electrolyte, and the positive electrode plate, the diaphragm and the electrolyte are not limited by the invention.
Hereinafter, the nano red phosphorus-porous carbon composite material, and the preparation method and application thereof will be further described by the following specific examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the present invention and should not be construed as limiting the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
Washing Chlorella with deionized water for several times to remove impurities, centrifuging and oven drying. After mixing 1.28g of sodium carbonate with 480mL of deionized water, adding 9mL of ethylenediamine solution and 100mg of commercial red phosphorus, dispersing uniformly, adding 0.60g of dried chlorella, stirring, gradually dropwise adding a mixed solution of ethanol and 0.05mol/L dilute hydrochloric acid (the volume ratio of ethanol to dilute hydrochloric acid is 1:20), stirring uniformly, and separating to obtain a first product.
The first product was carbonized at 1000 ℃ for 12h under nitrogen atmosphere to yield a second product.
400mg of commercial red phosphorus is dissolved in 35mL of ethylenediamine solution to obtain a second mixed solution, the second product is dispersed in a mixed solution of 5mL of ethanol and 100mL of dilute hydrochloric acid, the second mixed solution is stirred and added dropwise, and after full stirring, the mixture is filtered and freeze-dried to obtain the nano red phosphorus-porous carbon composite material.
Example 2
Washing Chlorella with deionized water for several times to remove impurities, centrifuging and oven drying. After mixing 1.35g of zinc chloride with 360mL of deionized water, adding 10mL of ethylenediamine solution and 100mg of commercial red phosphorus, dispersing uniformly, adding 0.30g of dried chlorella, stirring, gradually dropwise adding a mixed solution of ethanol and 0.05mol/L dilute hydrochloric acid (the volume ratio of ethanol to dilute hydrochloric acid is 1:20), stirring uniformly, and separating to obtain a first product.
The first product was carbonized at 1000 ℃ for 12h under nitrogen atmosphere to yield a second product.
400mg of commercial red phosphorus is dissolved in 35mL of ethylenediamine solution to obtain a second mixed solution, the second product is dispersed in a mixed solution of 5mL of ethanol and 100mL of dilute hydrochloric acid, the second mixed solution is stirred and added dropwise, and after full stirring, the mixture is filtered and freeze-dried to obtain the nano red phosphorus-porous carbon composite material.
Example 3
Washing Chlorella with deionized water for several times to remove impurities, centrifuging and oven drying. After mixing 1.28g of sodium carbonate with 480mL of deionized water, adding 9mL of ethylenediamine solution and 100mg of commercial red phosphorus, dispersing uniformly, adding 0.40g of dried chlorella, stirring, gradually dropwise adding a mixed solution of ethanol and 0.05mol/L dilute hydrochloric acid (the volume ratio of ethanol to dilute hydrochloric acid is 1:20), stirring uniformly, and separating to obtain a first product.
The first product was carbonized at 700 ℃ for 12h under nitrogen atmosphere to yield a second product.
400mg of commercial red phosphorus is dissolved in 35mL of ethylenediamine solution to obtain a second mixed solution, the second product is dispersed in a mixed solution of 5mL of ethanol and 100mL of dilute hydrochloric acid, the second mixed solution is stirred and added dropwise, and after full stirring, the mixture is filtered and freeze-dried to obtain the nano red phosphorus-porous carbon composite material.
Comparative example 1
Washing Chlorella with deionized water for several times to remove impurities, centrifuging and oven drying. After mixing 1.28g of sodium carbonate with 480mL of deionized water, 0.60g of dried chlorella was added, and the mixture was stirred and separated to obtain a first product.
Carbonizing the first product at 1000 ℃ for 12 hours in nitrogen atmosphere to obtain the chlorella-derived porous carbon.
400mg of commercial red phosphorus is dissolved in 35mL of ethylenediamine solution to obtain a mixed solution, chlorella-derived porous carbon is dispersed in 5mL of ethanol and 100mL of diluted hydrochloric acid, the mixed solution is stirred and added dropwise, and after full stirring, the mixture is filtered and freeze-dried to obtain the nano red phosphorus-porous carbon composite material.
Comparative example 2
Washing Chlorella with deionized water for several times to remove impurities, centrifuging and oven drying. After mixing 1.28g of sodium carbonate with 480mL of deionized water, 0.60g of dried chlorella was added, and the mixture was stirred and separated to obtain a first product.
Carbonizing the first product at 1000 ℃ for 12 hours in nitrogen atmosphere to obtain the chlorella-derived porous carbon.
400mg of commercial red phosphorus is dissolved in 35mL of ethylenediamine solution to obtain a mixed solution, chlorella-derived porous carbon is dispersed in a mixed solution of 5mL of ethanol and 100mL of dilute hydrochloric acid, the mixed solution is stirred and added dropwise, and the intermediate product is obtained after full stirring and filtration.
Carbonizing the intermediate product at 1000 ℃ for 12 hours in nitrogen atmosphere to obtain the nano red phosphorus-porous carbon composite material.
Comparative example 3
Washing Chlorella with deionized water for several times to remove impurities, centrifuging and oven drying. After mixing 1.28g of sodium carbonate with 480mL of deionized water, adding 9mL of ethylenediamine solution and 100mg of commercial red phosphorus, dispersing uniformly, adding 0.60g of dried chlorella, stirring, gradually dropwise adding a mixed solution of ethanol and 0.05mol/L dilute hydrochloric acid (the volume ratio of ethanol to dilute hydrochloric acid is 1:20), stirring uniformly, and separating to obtain a first product.
And carbonizing the first product at 1000 ℃ for 12 hours in nitrogen atmosphere to obtain the nano red phosphorus-porous carbon composite material.
Comparative example 4
Comparative example 4 differs from example 1 in that sodium carbonate was not added.
Comparative example 5
Comparative example 5 differs from example 1 in that 480mL of n-butanol was added instead of 480mL of deionized water.
Comparative example 6
Comparative example 6 differs from example 1 in that 480mL of diethyl ether was added instead of 480mL of deionized water.
The composites prepared in examples 1-3 and comparative examples 1-6 were tested and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the composite materials prepared in examples 1-3 all achieved red phosphorus deposition levels of about 38% -45%. In comparison with example 1, comparative example 1 did not deposit nano red phosphorus at the time of carbonization, resulting in nano red phosphorus being mainly distributed on the porous carbon surface layer, being difficult to enter inside, so that the deposition amount was lower than example 1, and a part of white phosphorus appeared; comparative example 2, in which liquid deposition was performed first and then carbonization was performed, was not as high in deposition amount as example 1 due to limited liquid deposition ability; comparative example 3 in which nano red phosphorus was deposited only by carbonization, the nano red phosphorus on the porous carbon surface layer was insufficient, resulting in a deposition amount lower than that of example 1; comparative example 4, in which no pore-forming agent was added, resulted in less pores of the carbon material, thereby affecting the deposition amount of nano red phosphorus; comparative example 5 and comparative example 6 use n-butanol or diethyl ether as a solvent, and since n-butanol or diethyl ether is not hydrophilic, the inside of the porous carbon is substantially void-free, nano red phosphorus cannot enter the inside of the porous carbon, and the nano red phosphorus deposition amount is low.
Application example
The composite materials prepared in examples 1-3 and comparative examples 1-6 were formulated into negative electrodes for button sodium ion batteries, specifically comprising: adding 90wt% of composite material, 5wt% of conductive agent and 5wt% of binder into N-methyl pyrrolidone (NMP), uniformly mixing, coating on aluminum foil, placing into a vacuum drying oven, drying at 80 ℃ for 12 hours, rolling and cutting baked electrode slices into small 12mm wafers, weighing, placing into a vacuum glove box, and assembling the button cell. A mixed solution of 1.0mol/L NaPF6 and 3.0% FEC Propylene Carbonate (PC) was used as an electrolyte, and a metallic sodium sheet was used as a counter electrode.
Electrochemical performance tests were performed on the batteries prepared in examples 1 to 3 and comparative examples 1 to 6, in which example 1 was cycled 500 times long cycle curve at a current density of 0.5A/g and 200 times long cycle curve at a current density of 0.2A/g, respectively, as shown in FIGS. 3 and 4, and test data for all examples and comparative examples were cycled 200 times at a current density of 0.2A/g, as shown in Table 2.
TABLE 2
As can be seen from FIG. 3, the specific discharge capacity of example 1 was reduced from 1438mAh/g for the first time to 1211mAh/g for the 20 th time at a current density of 0.5A/g for 500 cycles, and then was gradually smoothed. Even after 500 times of circulation, the specific discharge capacity still can reach 1193mAh/g, the first charge-discharge efficiency is 89.9%, and the discharge efficiency is stabilized at about 100% in the subsequent circulation, so that the ultra-high specific discharge capacity and the excellent circulation stability are shown.
As can be seen from FIG. 4, the specific discharge capacity of example 1 rapidly decreased from 1673mAh/g for the first time to 1366mAh/g under 200 cycles of current density of 0.2A/g, and then gradually smoothed. The specific discharge capacity can still reach 1327mAh/g even after 200 times of circulation, the first charge-discharge efficiency is 89.9%, and the specific discharge capacity is stabilized at 99.8% in the subsequent circulation, and the super-high specific discharge capacity and the excellent circulation stability are also shown.
According to Table 2, the specific capacity of the first discharge and the specific capacity after 200 cycles of examples 1-3 are better than those of comparative examples 1-6, which shows that the nano red phosphorus-porous carbon composite material provided by the invention can remarkably reduce the capacity attenuation phenomenon of nano red phosphorus caused by the volume deformation effect in the charge and discharge process, and can improve the electrochemical performance when being used as a cathode material for batteries.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The preparation method of the nano red phosphorus-porous carbon composite material is characterized by comprising the following steps of:
mixing a pore-forming agent, a solvent, an ethylenediamine solution and red phosphorus to obtain a first mixed solution, mixing chlorella with the first mixed solution, adding the first mixed solution into a first acidic solution, and separating to obtain a first product, wherein the solvent is selected from water and/or a hydrophilic solvent;
carbonizing the first product under the condition of protective gas to obtain a second product;
and mixing the second product with a second acidic solution, adding a second mixed solution, wherein the second mixed solution is a mixed solution of ethylenediamine solution and red phosphorus, and separating to obtain the nano red phosphorus-porous carbon composite material.
2. The method of preparing a nano red phosphorus-porous carbon composite according to claim 1, wherein the step of preparing the first product satisfies at least one of the following conditions:
(1) The mass ratio of the chlorella to the pore-forming agent to the solvent is 2 (4-15) (1-3);
(2) In the first mixed solution, the mass fraction of the red phosphorus is 2% -8%;
(3) In the first mixed solution, the mass fraction of the ethylenediamine solution is 6% -40%;
(4) The first acidic solution is added in a mode selected from the group consisting of batch addition;
(5) The pore-forming agent is at least one selected from sodium carbonate, potassium carbonate, zinc chloride, potassium acetate, sodium bicarbonate, potassium hydroxide, sodium hydroxide, calcium carbonate and calcium chloride;
(6) The hydrophilic solvent is at least one selected from sodium chloride solution, glucose syrup and ethanol.
3. The method for preparing a nano red phosphorus-porous carbon composite material according to claim 1, wherein the pH of the first acidic solution and the second acidic solution are each independently selected from 1.3 to 1.6.
4. The method for preparing a nano red phosphorus-porous carbon composite material according to claim 3, wherein the first acidic solution and the second acidic solution are each independently selected from ethanol solutions containing diluted hydrochloric acid, the volume ratio of ethanol to diluted hydrochloric acid in the ethanol solutions containing diluted hydrochloric acid is 1 (0.5-30), and the concentration of the diluted hydrochloric acid is 0.025mol/L-0.1mol/L.
5. The method of preparing a nano red phosphorus-porous carbon composite according to claim 1, wherein the step of mixing the second product with a second acidic solution and adding the second mixed solution satisfies at least one of the following conditions:
(1) In the second mixed solution, the concentration of red phosphorus is 4g/L-50g/L;
(2) The second mixed solution is added in a mode selected from the group consisting of batch addition.
6. The method for preparing the nano red phosphorus-porous carbon composite material according to claim 1, wherein the carbonization temperature is 400-1100 ℃ and the carbonization time is 0.5-30 h.
7. A nano red phosphorus-porous carbon composite material produced by the method for producing a nano red phosphorus-porous carbon composite material according to any one of claims 1 to 6, wherein the nano red phosphorus-porous carbon composite material comprises a porous carbon matrix and nano red phosphorus particles distributed in the porous carbon matrix.
8. The nano red phosphorus-porous carbon composite of claim 7, wherein the nano red phosphorus-porous carbon composite meets at least one of the following conditions:
(1) The particle size of the nano red phosphorus-porous carbon composite material is 2-10 mu m;
(2) The particle size of the nano red phosphorus particles is 5nm-10nm;
(3) The deposition amount of the nanometer red phosphorus particles in the nanometer red phosphorus-porous carbon composite material is 38% -45%.
9. A negative electrode tab comprising a negative electrode current collector and a negative electrode active material layer comprising the nano red phosphorus-porous carbon composite of any one of claims 7 or 8.
10. A battery comprising the negative electrode tab of claim 9.
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