CN114918426A - Block bismuth-carbon composite and preparation method and application thereof - Google Patents
Block bismuth-carbon composite and preparation method and application thereof Download PDFInfo
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- OLDOGSBTACEZFS-UHFFFAOYSA-N [C].[Bi] Chemical compound [C].[Bi] OLDOGSBTACEZFS-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 24
- IEVWNXLJUKRPPX-UHFFFAOYSA-N bismuth azane Chemical compound N.[Bi+3] IEVWNXLJUKRPPX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 claims abstract description 15
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 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 claims abstract description 8
- 238000010000 carbonizing Methods 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 8
- 239000010406 cathode material Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 238000000197 pyrolysis Methods 0.000 claims description 22
- 238000003763 carbonization Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 14
- 239000007773 negative electrode material Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 238000009656 pre-carbonization Methods 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 230000002441 reversible effect Effects 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000007431 microscopic evaluation Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C12/00—Alloys based on antimony or bismuth
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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 discloses a massive bismuth-carbon composite and a preparation method and application thereof, and relates to the technical field of energy materials and electrochemistry. The preparation method of the bulk bismuth-carbon composite comprises the following steps: (1) adding water to bismuth citrate, citric acid and ammonia water serving as raw materials for dissolving, and reacting to obtain a product mixed solution; (2) washing the product mixed liquor prepared in the step (1) by using a washing solution, centrifuging, and drying to obtain a white powdery bismuth ammonium salt complex; (3) and (3) pyrolyzing and carbonizing the white powdery bismuth ammonium salt complex prepared in the step (2) in an inert atmosphere to obtain the bismuth-carbon complex. The bulk bismuth-carbon composite prepared by the invention has excellent electrochemical performance as a sodium/potassium ion battery cathode material, has ultrahigh first efficiency, high specific capacity, excellent rate capability and stable cyclicity, has wide commercial application prospect, and is simple and easy to implement, mild and controllable in conditions, low in cost and suitable for popularization and use.
Description
Technical Field
The invention relates to the technical field of energy materials and electrochemistry, in particular to a massive bismuth-carbon compound and a preparation method and application thereof.
Background
In recent years, sodium/potassium ion batteries have become a new generation of energy storage technology due to their outstanding electrochemical performance, low price, safety and reliability. However, it remains a challenge to develop sodium/potassium storage materials with high specific capacity, high stability cycling, and high rate. The serious growth of dendrite is easily caused by the low sodium-insertion potential of the carbon material, so that the safety performance of the battery is reduced; the transition metal oxygen/sulfide material can generate a multi-step phase transformation process in the charging and discharging process, and the cycling stability of the battery is seriously influenced; the metal and alloy negative electrode material has proper potential (0.2-1.0V) and higher volume specific capacity, and has certain advantages. Among them, bismuth metal is considered as an ideal alloy negative electrode material due to its advantages of narrow band gap, high ionic conductivity, etc. However, when solvated sodium ions are deintercalated in the solid phase metal material, the volume of the material is drastically changed, and the material is easily crushed and separated from the current collector, thereby causing continuous degradation of performance. In addition, the inter-electrode interface also tends to induce thick, non-uniform, rather unstable Solid Electrolyte Interphase (SEI), resulting in too low first turn coulombic efficiency, resulting in capacity loss and cycle degradation.
Therefore, those skilled in the art have been devoted to develop a high-performance anode material having a high stable cycle with a suitable potential, a high first-pass, and a rapid charge and discharge capability.
Disclosure of Invention
In view of the above defects in the prior art, the technical problems to be solved by the invention are the problems of low specific capacity, low coulombic efficiency, poor cycle and the like of the conventional negative electrode material of the sodium/potassium ion battery, and the invention provides a bulk bismuth-carbon composite and a preparation method and application thereof, wherein the synthesized bulk bismuth-carbon composite has high first efficiency, high specific capacity, excellent rate capability and stable cyclicity, thereby showing the huge application prospect in the field of energy storage and being suitable for the negative electrode material of the sodium/potassium ion battery; and the performance of the bismuth-carbon composite can be expected to be improved to the commercial application level through morphology control, binder optimization and electrolyte optimization at the later stage of the process.
In order to achieve the technical purpose, the invention is mainly realized by the following technical scheme:
the invention provides a preparation method of a blocky bismuth-carbon composite, which comprises the following steps:
(1) adding water to bismuth citrate, citric acid and ammonia water serving as raw materials for dissolving, and reacting to obtain a product mixed solution;
(2) washing the product mixed liquor prepared in the step (1) by using a washing solution, centrifuging, and drying to obtain a white powdery bismuth ammonium salt complex;
(3) and (3) pyrolyzing and carbonizing the white powdery bismuth ammonium salt complex prepared in the step (2) in an inert atmosphere to obtain the bismuth-carbon complex.
In the step (1), ammonia water may be replaced by ammonia gas, or ammonia water containing ammonia gas may be used instead of ammonia water.
In the invention, in the step (1), the specific preparation steps of the product mixed solution comprise: putting bismuth citrate and citric acid into a three-necked bottle, adding water to fully dissolve, reacting at 80-100 ℃, cooling to room temperature after the reaction is completed, adding an ammonia water solution under stirring, and continuing to react at room temperature for 4-8h, wherein the solution is changed from clear to turbid in the reaction process and is generated along with white precipitate; then carrying out curing reaction for 10h to obtain a product mixed solution.
In a preferred embodiment of the present invention, in the step (2), the washing solution is water or ethanol, the product is washed with water and ethanol for 3 times respectively until the centrifuged supernatant gradually becomes clear, the solid is collected, then the solid is placed in an oven and dried at 80 ℃ for 6 hours, and the white powdery bismuth ammonium salt complex is collected.
Further, in the step (3), the inert atmosphere is nitrogen or argon, the pyrolysis carbonization temperature is 800-.
In another preferred embodiment of the present invention, before the step (3) of performing the pyrolysis carbonization reaction, a pre-carbonization process is further included, wherein the pre-carbonization process includes: firstly heating in an inert atmosphere in a tubular furnace at a heating rate of 2 ℃/min, carrying out pre-carbonization reaction after heating to 350 ℃, wherein the reaction time is not more than 8h, and then heating to carry out pyrolysis carbonization reaction.
The invention also provides a bulk bismuth-carbon composite which is mainly prepared by the preparation method of the bulk bismuth-carbon composite.
Preferably, the diameter of the bulk bismuth-carbon composite is 9-12 μm.
In addition, the invention provides an application of the bulk bismuth-carbon composite or the bulk bismuth-carbon composite prepared by the preparation method in preparation of a cathode material of a sodium/potassium ion battery.
Further, the first reversible capacity of the block-shaped bismuth-carbon composite is 314.2-417.2mAh/g and the first efficiency is 50-95% when the block-shaped bismuth-carbon composite is used for preparing a sodium ion battery cathode material; the capacity is not lower than 111.8mAh/g under the current density of 5A/g; in ether electrolyte, under the current density of 20A/g, the capacity is not lower than 187.7 mAh/g; under the condition of circulation of 5A/g for 2000 times, the capacity retention rate is 88.5 percent; the first reversible capacity of the blocky bismuth-carbon composite is 385.2-445.6mAh/g when the blocky bismuth-carbon composite is used for preparing a potassium ion battery cathode material, and the first efficiency is 76-96%; the capacity is not lower than 395.3mAh/g under the current density of 2A/g; in ether electrolyte, under the current density of 10A/g, the capacity is not lower than 384.2 mAh/g; under the condition of 800 cycles of 2A/g, the capacity retention rate is 73.2 percent.
Compared with the prior art, the invention has the following beneficial effects:
1. the bulk bismuth-carbon composite prepared by the invention has excellent electrochemical performance as a sodium/potassium ion battery cathode material, has ultrahigh first-time efficiency, high specific capacity, excellent rate capability and stable cyclicity, and has wide commercial application prospect;
2. the method is simple and easy to implement, mild and controllable in conditions, low in cost and suitable for popularization and use.
Drawings
The conception, specific structure and technical effects of the present invention will be further described in conjunction with the accompanying drawings to fully understand the purpose, characteristics and effects of the present invention.
FIG. 1 is an SEM photograph of bismuth ammonium salt complexes of examples 1-3 of the present invention.
Fig. 2 is an SEM image of the bulk bismuth-carbon composite of examples 1-3 of the present invention.
Fig. 3 is an XRD pattern of the bulk bismuth-carbon composite of examples 1-3 of the present invention.
Fig. 4 is a Raman chart of the bulk bismuth-carbon composite of examples 1-3 of the present invention.
Fig. 5 is a graph of the impedance of the bulk bismuth-carbon composite of examples 1-3 of the present invention.
Fig. 6 is a graph of the cycle performance of the sodium ion battery of the bulk bismuth-carbon composite of example 3 of the invention.
Fig. 7 is a graph of the rate performance of the sodium ion battery of the bulk bismuth-carbon composite of example 3 of the invention.
Fig. 8 is a graph showing the charge and discharge curves of the sodium ion battery of the bulk bismuth-carbon composite of example 3 of the present invention.
Fig. 9 is a graph of the cycle performance of the potassium ion battery of the bulk bismuth carbon composite of example 3 of the invention.
Fig. 10 is a graph of the rate performance of the potassium ion battery of the bulk bismuth carbon composite of example 3 of the invention.
Fig. 11 is a charge-discharge curve diagram of a potassium ion battery of the bulk bismuth-carbon composite of example 3 of the present invention.
Detailed Description
The technical contents of the preferred embodiments of the present invention will be more clearly and easily understood by referring to the drawings attached to the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
Example 1
In this embodiment, a method for preparing a bulk bismuth-carbon composite includes the following steps:
(1) weighing 7.9616g of bismuth citrate and 1.9214g of citric acid in a three-necked bottle, adding 40mL of water to fully dissolve the bismuth citrate and the citric acid, reacting at 80-100 ℃ for 1h, cooling the temperature to room temperature, adding 20mL of ammonia water solution under stirring to react for 4-8h, wherein the solution is changed from clear to turbid in the reaction process and white precipitate is generated; then carrying out curing reaction for 10 hours to obtain a product mixed solution;
(2) centrifuging the product mixed solution, collecting a white product in the product mixed solution, washing the product with water and ethanol for 3 times respectively until the centrifuged supernatant becomes clear gradually, collecting a solid matter, then placing the solid matter in a drying oven, drying for 6 hours at the temperature of 80 ℃, and collecting the white powdery bismuth ammonium salt complex;
(3) and (3) putting 2.0g of the white powder prepared in the step (2) into a crucible, heating in an inert atmosphere in a tubular furnace at a heating rate of 2 ℃/min under an argon atmosphere, pre-carbonizing at 350 ℃ for 1h, then continuously heating to perform a pyrolysis carbonization reaction, wherein the pyrolysis carbonization temperature is 800 ℃, the heating rate is 5 ℃/min, and the pyrolysis carbonization time is 2h, so as to obtain the bismuth-carbon composite.
Experimental test analysis:
the results of microscopic analysis and physical property examination of the bismuth ammonium salt complex and the bismuth carbon complex prepared by the method of example 1 are shown in fig. 1 to 11, respectively.
FIG. 1 is a scanning electron micrograph of the bismuth ammonium salt complex of example 1, wherein the organic cake has a diameter of 38 μm.
Fig. 2 shows a scanning electron micrograph of the bismuth-carbon composite, which has a diameter of 12 μm.
FIG. 3 is an XRD pattern of a bismuth-carbon composite, all peaks are well matched to the hexagonal bismuth phase with R-3m space group (JCPDS:85-1329) and no impurity signal peaks are seen, indicating complete conversion to Bi. In addition, the XRD pattern did not show a distinct carbon peak, indicating that the carbon structure is amorphous. These peaks and high intensity peaks illustrate the high crystallinity of Bi in the bismuth-carbon composite.
Amplitude ratio (I) of D and G peaks of bismuth-carbon composite in FIG. 4 D /I G ) Is 1.24, indicating that the amorphous carbon matrix contains many defects and vacancies.
Fig. 5 is an impedance plot of a bismuth-carbon composite, further investigating its charge transfer kinetics.
FIG. 6 is a graph of cycling performance at 5A/g current density in a sodium ion battery, with a specific discharge capacity of 225.1mAh/g after 2000 cycles.
Fig. 7 is a graph of cycle performance of the sodium ion battery at different current densities, and it can be seen from the graph that there is almost no capacity fading at different rates, and the specific capacity can also reach 309.8mAh/g at a current density of 20A/g, and it can be seen that the battery has very excellent rate performance.
FIG. 8 is a graph showing the charge and discharge curves of the sodium ion battery in the 1 st and 2 nd circles, wherein the charge and discharge current density is 1A/g, the charge and discharge capacity of the first circle is 438.2/348.9mAh/g, and the coulombic efficiency of the first circle is 79.6%.
As can be seen from fig. 6 to 11, the bismuth-carbon composite prepared by the method of this embodiment has an ultra-high first efficiency, a high specific capacity, an excellent rate capability, and a stable cyclicity, and has a wide commercial application prospect.
Example 2
In this embodiment, a method for preparing a bulk bismuth-carbon composite includes the following steps:
in this embodiment, a method for preparing a bulk bismuth-carbon composite includes the following steps:
(1) weighing 7.9616g of bismuth citrate and 1.9214g of citric acid in a three-necked bottle, adding 40mL of water to fully dissolve the bismuth citrate and the citric acid, reacting at 80-100 ℃ for 1h, cooling the temperature to room temperature, adding 20mL of ammonia water solution under stirring to react for 4-8h, wherein the solution is changed from clear to turbid in the reaction process and white precipitate is generated; then carrying out curing reaction for 10 hours to obtain a product mixed solution;
(2) centrifuging the product mixed solution, collecting a white product in the product mixed solution, respectively washing the product with water and ethanol for 3 times until the centrifuged supernatant is gradually clarified, collecting a solid matter, then placing the solid matter in a drying oven, drying for 6 hours at the temperature of 80 ℃, and collecting the white powdery bismuth ammonium salt complex;
(3) and (3) putting 2.0g of the white powder prepared in the step (2) into a crucible, heating in an inert atmosphere in a tubular furnace at a heating rate of 2 ℃/min under an argon atmosphere, pre-carbonizing at 350 ℃ for 1h, then continuously heating to perform a pyrolysis carbonization reaction, wherein the pyrolysis carbonization temperature is 900 ℃, the heating rate is 5 ℃/min, and the pyrolysis carbonization time is 2h, so as to obtain the bismuth-carbon composite.
Experimental test analysis:
microscopic analysis and physical property examination were performed on the bismuth ammonium salt complex and the bismuth carbon complex prepared by the method of example 2.
FIG. 1 is a scanning electron micrograph of the bismuth ammonium salt complex of this example, and the diameter of the organic cake was 38 μm.
Fig. 2 shows the scanning electron microscope image of the bismuth-carbon composite, which has a diameter of 9 μm.
FIG. 3 is an XRD pattern of a bismuth-carbon composite, all peaks are well matched to the hexagonal bismuth phase with R-3m space group (JCPDS:85-1329), and no impurity signal peak is seen, indicating complete conversion to Bi. In addition, the XRD pattern did not show a distinct carbon peak, indicating that the carbon structure is amorphous. These peaks and high intensity peaks illustrate the high crystallinity of Bi in the bismuth-carbon composite.
Amplitude ratio (I) of D and G peaks of bismuth-carbon composite in FIG. 4 D /I G ) 1.00, indicating that the amorphous carbon matrix contains many defects and vacancies.
Fig. 5 is an impedance plot of a bismuth-carbon composite, further investigating its charge transfer kinetics.
FIG. 6 is a graph of cycling performance at 5A/g current density in a sodium ion battery, with a specific discharge capacity of 361.9mAh/g after 2000 cycles.
Fig. 7 is a cycle performance diagram of the sodium ion battery under different current densities, and it can be seen from the diagram that the capacity under different multiplying factors hardly attenuates, and the specific capacity can also reach 387.5mAh/g under the current density of 20A/g, and it can be seen that the battery has very excellent multiplying factor performance.
FIG. 8 is a graph showing the charge and discharge curves of the 1 st and 2 nd circles in a sodium ion battery, wherein the charge and discharge current density is 1A/g, the charge and discharge capacity of the first circle is 440.1/417.2mAh/g, and the coulombic efficiency of the first circle is 94.8%.
FIG. 9 is a graph of cycle performance at a current density of 2A/g in a potassium ion battery, and the specific discharge capacity after 800 cycles was 399.8 mAh/g.
Fig. 10 is a graph of cycle performance at different current densities in a potassium ion battery, from which it can be seen that there is little decay in capacity from different rates, and it can be seen that the battery has very excellent rate performance.
FIG. 11 is a graph showing the charge and discharge curves of the 1 st and 2 nd circles in a potassium ion battery, wherein the charge and discharge current density is 1A/g, the charge and discharge capacity of the first circle is 501.6/401.3mAh/g, and the coulombic efficiency of the first circle is 80.0%.
As can be seen from fig. 6-11, the bismuth-carbon composite prepared by the method of this embodiment has an ultra-high first efficiency, a high specific capacity, an excellent rate capability, and a stable cyclicity, and has a wide commercial application prospect.
Example 3
In this embodiment, a method for preparing a bulk bismuth-carbon composite includes the following steps:
in this embodiment, a method for preparing a bulk bismuth-carbon composite includes the following steps:
(1) weighing 7.9616g of bismuth citrate and 1.9214g of citric acid in a three-necked bottle, adding 40mL of water to fully dissolve the bismuth citrate and the citric acid, reacting at 80-100 ℃ for 1h, cooling the temperature to room temperature, adding 20mL of ammonia water solution under stirring to react for 4-8h, wherein the solution is changed from clear to turbid in the reaction process and white precipitate is generated; then carrying out curing reaction for 10 hours to obtain a product mixed solution;
(2) centrifuging the product mixed solution, collecting a white product in the product mixed solution, washing the product with water and ethanol for 3 times respectively until the centrifuged supernatant becomes clear gradually, collecting a solid matter, then placing the solid matter in a drying oven, drying for 6 hours at the temperature of 80 ℃, and collecting the white powdery bismuth ammonium salt complex;
(3) and (3) putting 2.0g of the white powder prepared in the step (2) into a crucible, heating in an inert atmosphere in a tubular furnace at a heating rate of 2 ℃/min under an argon atmosphere, pre-carbonizing at 350 ℃ for 1h, then continuously heating to perform a pyrolysis carbonization reaction at a pyrolysis carbonization temperature of 1000 ℃, a heating rate of 5 ℃/min and a pyrolysis carbonization time of 2h to obtain the bismuth-carbon composite.
Experimental test analysis:
microscopic analysis and physical property examination were performed on the bismuth ammonium salt complex and the bismuth carbon complex prepared by the method of example 3.
FIG. 1 is a scanning electron micrograph of the bismuth ammonium salt complex of this example, and the organic lumps had a diameter of 38 μm.
Fig. 2 shows the scanning electron microscope image of the bismuth-carbon composite, which has a diameter of 11 μm.
FIG. 3 is an XRD pattern of a bismuth-carbon composite, all peaks are well matched to the hexagonal bismuth phase with R-3m space group (JCPDS:85-1329) and no impurity signal peaks are seen, indicating complete conversion to Bi. In addition, the XRD pattern did not show a distinct carbon peak, indicating that the carbon structure is amorphous. These peaks and high intensity peaks illustrate the high crystallinity of Bi in the bismuth-carbon composite.
Amplitude ratio (I) of D and G peaks of bismuth-carbon composite in FIG. 4 D /I G ) 0.93, indicating that the amorphous carbon matrix contains many defects and vacancies.
Fig. 5 is an impedance plot of a bismuth-carbon composite, further investigating its charge transfer kinetics.
FIG. 6 is a graph of cycling performance at a current density of 5A/g in a sodium ion battery, and after 2000 cycles, the specific discharge capacity is 111.8mAh/g.
Fig. 7 is a graph of cycle performance at different current densities in a sodium ion battery, and it can be seen from the graph that the capacity hardly decays at different rates, and the specific capacity can reach 187.7mAh/g at a current density of 20A/g, and it can be seen that the battery has very excellent rate performance.
FIG. 8 is a graph showing the charge and discharge curves of the 1 st and 2 nd circles in a sodium ion battery, wherein the charge and discharge current density is 1A/g, the charge and discharge capacity of the first circle is 652.4/314.2mAh/g, and the coulombic efficiency of the first circle is 50.3%.
As can be seen from fig. 6-11, the bismuth-carbon composite prepared by the method of this embodiment has an ultra-high first efficiency, a high specific capacity, an excellent rate capability, and a stable cyclicity, and has a wide commercial application prospect.
Comparative example 1
In this comparative example, a method of preparing a bulk bismuth-carbon composite includes the steps of:
(1) weighing 7.9616g of bismuth citrate and 1.9214g of citric acid in a three-necked bottle, adding 40mL of water to fully dissolve the bismuth citrate and the citric acid, reacting at 80-100 ℃ for 1h, cooling the temperature to room temperature, adding 20mL of ammonia water solution under stirring to react for 4-8h, wherein the solution is changed from clear to turbid in the reaction process and white precipitate is generated; then carrying out curing reaction for 10 hours to obtain a product mixed solution;
(2) centrifuging the product mixed solution, collecting a white product in the product mixed solution, respectively washing the product with water and ethanol for 3 times until the centrifuged supernatant is gradually clarified, collecting a solid matter, then placing the solid matter in a drying oven, drying for 6 hours at the temperature of 80 ℃, and collecting the white powdery bismuth ammonium salt complex;
(3) and (3) putting 2.0g of the white powder prepared in the step (2) into a crucible, heating in an inert atmosphere in a tubular furnace at a heating rate of 2 ℃/min under an argon atmosphere, pre-carbonizing at 350 ℃ for 1h, then continuously heating to perform a pyrolysis carbonization reaction at a pyrolysis carbonization temperature of 600 ℃, a heating rate of 5 ℃/min and a pyrolysis carbonization time of 2h to obtain the bismuth-carbon composite.
By carrying out inspection and test on the bismuth-carbon composite prepared in the comparative example 1, the result shows that when the bismuth-carbon composite is used as a sodium ion battery cathode material, the capacity is slightly attenuated under different multiplying powers, the specific capacity is 267.7mAh/g, the charge-discharge current density is 1A/g, the first-turn charge-discharge capacity is 369.5/282.1mAh/g, and the first-turn coulombic efficiency is 43.8%. The charge and discharge capacity and coulombic efficiency of the bismuth-carbon composite prepared in comparative example 1 were relatively poor compared to those of the bismuth-carbon composites prepared in examples 1 to 3.
Comparative example 2
In this comparative example, a method of preparing a bulk bismuth-carbon composite includes the steps of:
(1) weighing 7.9616g of bismuth citrate and 1.9214g of citric acid in a three-necked bottle, adding 40mL of water to fully dissolve the bismuth citrate and the citric acid, reacting at 80-100 ℃ for 1h, cooling the temperature to room temperature, adding 20mL of ammonia water solution under stirring to react for 4-8h, wherein the solution is changed from clear to turbid in the reaction process and white precipitate is generated; then carrying out curing reaction for 10 hours to obtain a product mixed solution;
(2) centrifuging the product mixed solution, collecting a white product in the product mixed solution, respectively washing the product with water and ethanol for 3 times until the centrifuged supernatant is gradually clarified, collecting a solid matter, then placing the solid matter in a drying oven, drying for 6 hours at the temperature of 80 ℃, and collecting the white powdery bismuth ammonium salt complex;
(3) and (3) putting 2.0g of the white powder prepared in the step (2) into a crucible, heating in an inert atmosphere in a tubular furnace at a heating rate of 2 ℃/min under an argon atmosphere, pre-carbonizing at 350 ℃ for 1h, then continuously heating to perform a pyrolysis carbonization reaction at a pyrolysis carbonization temperature of 1200 ℃, at a heating rate of 5 ℃/min and for 2h to obtain the bismuth-carbon composite.
By performing inspection and test on the bismuth-carbon composite prepared in the comparative example 2, the result shows that when the bismuth-carbon composite is used as a negative electrode material of a sodium ion battery, the capacity is hardly attenuated under different multiplying powers, but under the current density of 20A/g, the specific capacity is only 96.3mAh/g, the charge-discharge current density is 1A/g, the charge-discharge capacity of the first circle is 396.4/287.2mAh/g, and the coulombic efficiency of the first circle is 48.3%. Compared with the bismuth-carbon composites prepared in examples 1 to 3, the bismuth-carbon composite prepared in comparative example 2 has relatively poor charge-discharge capacity and coulombic efficiency.
In summary, the method of the embodiment uses the bismuth ammonium salt complex as the precursor to prepare the bismuth-based negative electrode material, and has the advantages of simple preparation process, mild pyrolysis conditions and low cost. The diameter and the like of the massive bismuth carbon material can be adjusted by adjusting the reaction temperature, the pyrolysis temperature, the heating rate, the time and the like, so that the bismuth carbon negative electrode material with the optimal electrochemical performance is obtained.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions that can be obtained by a person skilled in the art through logical analysis, reasoning or limited experiments based on the prior art according to the concepts of the present invention should be within the scope of protection determined by the claims.
Claims (10)
1. The preparation method of the massive bismuth-carbon composite is characterized by comprising the following steps:
(1) adding water to dissolve bismuth citrate, citric acid and ammonia water serving as raw materials, and reacting to obtain a product mixed solution;
(2) washing the product mixed liquor prepared in the step (1) by using a washing solution, centrifuging, and drying to obtain a white powdery bismuth ammonium salt complex;
(3) pyrolyzing and carbonizing the white powdery bismuth ammonium salt complex prepared in the step (2) in an inert atmosphere to obtain the bismuth-carbon complex.
2. The method for preparing a bulk bismuth carbon composite according to claim 1, wherein in the step (1), ammonia gas may be used instead of ammonia gas.
3. The method for preparing a bulk bismuth carbon composite according to claim 1, wherein in the step (1), the specific preparation step of the product mixture solution comprises: putting bismuth citrate and citric acid into a three-necked bottle, adding water to fully dissolve, reacting at 80-100 ℃, cooling to room temperature after the reaction is completed, adding an ammonia water solution under stirring, and continuing to react at room temperature for 4-8h, wherein the solution is changed from clear to turbid in the reaction process and is generated along with white precipitate; then carrying out curing reaction for 10h to obtain a product mixed solution.
4. The method for preparing the bulk bismuth-carbon composite according to claim 1, wherein in the step (2), the washing solution is water or ethanol, the product is washed 3 times with water and ethanol respectively until the supernatant after centrifugation gradually becomes clear, the solid is collected, then the solid is placed in an oven and dried at 80 ℃ for 6 hours, and the white powdery bismuth ammonium salt complex is collected.
5. The method for preparing the bulk bismuth-carbon composite according to claim 1, wherein in the step (3), the inert atmosphere is nitrogen or argon, the pyrolysis carbonization temperature is 800-.
6. The method for preparing a bulk bismuth-carbon composite according to claim 1, wherein the step (3) further comprises a pre-carbonization process before the pyrolysis carbonization reaction, wherein the pre-carbonization process comprises: firstly heating in an inert atmosphere in a tubular furnace at a heating rate of 2 ℃/min, carrying out pre-carbonization reaction after heating to 350 ℃, wherein the reaction time is not more than 8h, and then heating to carry out pyrolysis carbonization reaction.
7. A bulk bismuth-carbon composite produced by the method for producing a bulk bismuth-carbon composite according to any one of claims 1 to 6.
8. The bulk bismuth-carbon composite of claim 7, wherein the bulk bismuth-carbon composite has a diameter of 9 to 12 μm.
9. Use of the bulk bismuth-carbon composite according to any one of claims 7 to 8 or the bulk bismuth-carbon composite prepared by the method according to any one of claims 1 to 6 for preparing a negative electrode material for a sodium/potassium ion battery.
10. The use of claim 9, wherein the bulk bismuth carbon composite has a first reversible capacity of 314.2-417.2mAh/g and a first efficiency of 50-95% in the preparation of a negative electrode material for a sodium ion battery; the capacity is not lower than 111.8mAh/g under the current density of 5A/g; in ether electrolyte, under the current density of 20A/g, the capacity is not lower than 187.7 mAh/g; under the condition of circulation of 5A/g for 2000 times, the capacity retention rate is 88.5 percent; the first reversible capacity of the blocky bismuth-carbon composite is 385.2-445.6mAh/g when the blocky bismuth-carbon composite is used for preparing a potassium ion battery cathode material, and the first efficiency is 76-96%; the capacity is not lower than 395.3mAh/g under the current density of 2A/g; in ether electrolyte, under the current density of 10A/g, the capacity is not lower than 384.2 mAh/g; under the condition of 800 cycles of 2A/g, the capacity retention rate is 73.2 percent.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2415192A1 (en) * | 1977-12-22 | 1979-08-17 | Uranerz Usa Inc | Extn. of uranium in situ from its ores - by oxidn. and leaching with oxygen enriched water under carbon di:oxide pressure and alkaline earth (bi)carbonate soln. |
| CN102600829A (en) * | 2012-02-17 | 2012-07-25 | 重庆工商大学 | Bismuth series photocatalyst, and preparation method thereof |
| CN108328599A (en) * | 2018-01-30 | 2018-07-27 | 东莞理工学院 | A method of nitrogen-doped porous carbon material is prepared based on citric acid transition/alkali metal complex salt |
| CN112126403A (en) * | 2020-09-28 | 2020-12-25 | 无锡博锦高分子研究发展有限公司 | Bonding composition for solar back panel and adhesive thereof |
| CN113321199A (en) * | 2021-03-04 | 2021-08-31 | 上海大学 | Polybenzoxazine-co-cresol-based polymer-derived hard carbon microspheres, and preparation method and application thereof |
| CN113736419A (en) * | 2021-10-19 | 2021-12-03 | 杭州之江新材料有限公司 | Double-component polyurethane heat-conducting structural adhesive and preparation method thereof |
-
2022
- 2022-05-27 CN CN202210593421.4A patent/CN114918426A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2415192A1 (en) * | 1977-12-22 | 1979-08-17 | Uranerz Usa Inc | Extn. of uranium in situ from its ores - by oxidn. and leaching with oxygen enriched water under carbon di:oxide pressure and alkaline earth (bi)carbonate soln. |
| CN102600829A (en) * | 2012-02-17 | 2012-07-25 | 重庆工商大学 | Bismuth series photocatalyst, and preparation method thereof |
| CN108328599A (en) * | 2018-01-30 | 2018-07-27 | 东莞理工学院 | A method of nitrogen-doped porous carbon material is prepared based on citric acid transition/alkali metal complex salt |
| CN112126403A (en) * | 2020-09-28 | 2020-12-25 | 无锡博锦高分子研究发展有限公司 | Bonding composition for solar back panel and adhesive thereof |
| CN113321199A (en) * | 2021-03-04 | 2021-08-31 | 上海大学 | Polybenzoxazine-co-cresol-based polymer-derived hard carbon microspheres, and preparation method and application thereof |
| CN113736419A (en) * | 2021-10-19 | 2021-12-03 | 杭州之江新材料有限公司 | Double-component polyurethane heat-conducting structural adhesive and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 钟威豪: "新型碳材料和铋材料的设计制备及其在钠离子电池中的应用", 广东工业大学硕士论文, 16 February 2022 (2022-02-16), pages 50 - 62 * |
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