CN113571682A - Bismuth/carbon composite material and preparation method and application thereof - Google Patents
Bismuth/carbon composite material and preparation method and application thereof Download PDFInfo
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 108
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000004132 cross linking Methods 0.000 claims abstract description 23
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 19
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 6
- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 5
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- RLWWKAGRZATJDC-UHFFFAOYSA-L tris(2-methylphenyl)bismuth(2+);dichloride Chemical compound CC1=CC=CC=C1[Bi](Cl)(Cl)(C=1C(=CC=CC=1)C)C1=CC=CC=C1C RLWWKAGRZATJDC-UHFFFAOYSA-L 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- -1 p-dichlorobenzyl Chemical group 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000007772 electrode material Substances 0.000 abstract description 8
- 239000010406 cathode material Substances 0.000 abstract description 3
- 238000005275 alloying Methods 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 238000007599 discharging Methods 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000010277 constant-current charging Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Images
Classifications
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- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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 belongs to the technical field of preparation of electrode materials of sodium-ion batteries, and particularly relates to a bismuth/carbon composite material and a preparation method and application thereof. Grinding and uniformly mixing an aromatic bismuth source, a cross-linking agent and a catalyst, then carrying out a cross-linking reaction, and purifying and drying after the cross-linking reaction is finished; and finally, carbonizing at 600-1600 ℃ in an inert gas atmosphere to obtain the bismuth/carbon composite material. The bismuth/carbon composite material prepared by the invention has the following advantages: on the one hand, bismuth has a high energy density as a metal material for alloying reactions. On the other hand, the carbon wrapped around bismuth mitigates volume expansion of the electrode material during charge and discharge. The composite material is further used for preparing a sodium ion battery cathode material, and has high energy density and long cycle stability.
Description
Technical Field
The invention belongs to the technical field of preparation of electrode materials of sodium-ion batteries, and particularly relates to a bismuth/carbon composite material and a preparation method and application thereof.
Background
The commercialization of lithium ion batteries in the 90 s of the 20 th century makes up the disadvantage that clean energy cannot be applied to power grid energy storage in a large scale due to intermittency, and has become the leading edge of the development of power grid energy storage technology in recent years. However, lithium is highly non-uniform and has limited reserves on earth, resulting in high lithium prices, which shade future applications of lithium ion batteries. Recently, sodium ion batteries have been widely studied. As an alternative material for lithium ion batteries, sodium has the advantages of low price, little influence from resource limitations, and chemical properties similar to those of lithium.
The key to commercialization of sodium ion batteries is the development of suitable negative electrode materials. Because the radius of sodium ions is larger than that of lithium ions, and a sodium-graphite intercalation compound cannot exist stably, graphite which is widely used as a negative electrode material of a commercial lithium ion battery cannot meet the capacity requirement of the sodium ion battery. In response to this problem, alloyed negative electrode materials (such as antimony, bismuth, and tin) having high theoretical capacity and high energy density are favored by more researchers. Wherein, bismuth has a density as high as 3800mAh cm-3And less volume change during cycling (relative to antimony and tin), is one of the most promising alloying anode materials. However, the bismuth elementary substance undergoes drastic volume change in the charging and discharging processes, so that the electrode is cracked and pulverized, the cycling stability of the bismuth elementary substance is poor, and the bismuth elementary substance is difficult to obtain the practical application value.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention provides a preparation method of a bismuth/carbon composite material, which can relieve the structural damage of volume expansion of bismuth to an electrode material in the charge and discharge process through coating the bismuth by carbon, thereby improving the stability of the electrode material.
The invention also aims to provide the bismuth/carbon composite material prepared by the preparation method, which has high energy density, high rate performance and excellent cycling stability.
The invention also aims to provide application of the bismuth/carbon composite material.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a bismuth/carbon composite material comprises the following steps:
(1) grinding and uniformly mixing an aromatic bismuth source and a cross-linking agent according to a molar ratio of (1:2) - (1:10), adding a catalyst, continuously grinding, and uniformly mixing to obtain a mixture;
(2) carrying out crosslinking reaction on the mixture ground and uniformly mixed in the step (1) at the temperature of 60-100 ℃ for 10-24 h, purifying and collecting a sample after the crosslinking reaction is finished, and drying to obtain a crosslinked product;
(3) carbonizing the crosslinked product prepared in the step (2) at 600-1600 ℃ for 2-12 h in an inert gas atmosphere to obtain a bismuth/carbon composite material;
the aromatic bismuth source in the step (1) is at least one of triphenyl bismuth, tri-o-tolyl bismuth dichloride and other organic metal compounds containing aromatic rings and bismuth atoms;
the cross-linking agent in the step (1) is at least one of terephthaloyl chloride, phthaloyl chloride, carbon tetrachloride, dimethoxymethane, 1, 2-dichloroethane and p-dichlorobenzyl;
the catalyst in the step (1) is at least one of anhydrous aluminum trichloride, anhydrous ferric trichloride and anhydrous stannic chloride;
the mass ratio of the aromatic bismuth source to the catalyst in the step (1) is preferably (1:0.5) to (1: 5);
the crosslinking reaction in the step (2) is preferably carried out in a constant-temperature drying oven;
the purification mode in the step (2) is preferably suction filtration;
the inert gas atmosphere in the step (3) is preferably nitrogen or argon;
the temperature of the carbonization treatment in the step (3) is preferably 5 ℃ min-1The temperature rising rate is 600-1600 ℃, and then the temperature is kept for 2-12 h;
a bismuth/carbon composite material prepared by the preparation method;
the bismuth/carbon composite material is applied to the field of sodium ion battery preparation;
the bismuth/carbon composite material is applied to the field of preparation of cathode materials of sodium ion batteries;
a bismuth/carbon composite electrode plate comprises the bismuth/carbon composite material;
the bismuth/carbon composite electrode plate preferably further comprises conductive carbon black and PVDF;
the mass ratio of the bismuth/carbon composite material to the conductive carbon black to the PVDF is preferably (6-8): 1-3): 1;
the preparation method of the bismuth/carbon composite electrode plate comprises the following steps:
mixing the bismuth/carbon composite material, conductive carbon black, PVDF and N-methyl pyrrolidone to prepare slurry, then coating the slurry on a copper foil, drying and rolling to obtain a bismuth/carbon composite material electrode slice;
the principle of the invention is as follows:
according to the invention, the aromatic bismuth source, the cross-linking agent and the catalyst are uniformly mixed by grinding, then under the action of the catalyst, the aromatic bismuth source and the cross-linking agent generate Friedel-crafts cross-linking reaction, and a cross-linking product is further carbonized at high temperature to obtain the bismuth/carbon composite material, wherein the bismuth is wrapped by carbon in the bismuth/carbon composite material, so that the structural damage of volume expansion of bismuth to an electrode material in the charge-discharge process can be relieved, and the stability of the electrode material is improved.
Compared with the prior art, the invention has the following advantages and effects:
the invention realizes the high-performance sodium ion battery cathode material based on the structural design, and the volume expansion of bismuth in the charging and discharging process is buffered by the coating of carbon, so that the stability of the electrode material is improved; the defect of low reversible capacity of carbon is neutralized by the presence of bismuth, and the bismuth and the carbon are cooperated, so that the bismuth/carbon composite material prepared by the invention has excellent cycle stability, rapid rate response capability and high energy density.
Drawings
Fig. 1 is an XRD pattern of the bismuth/carbon composite material prepared in example 1.
FIG. 2 shows the concentration of 1000mA g in the Bi/C composite assembled Na-ion battery prepared in example 1-1Current density of (c) cycle constant current charge-discharge diagram of 40 cycles.
FIG. 3 shows the concentration of 1000mA g in the Bi/C composite assembled Na-ion battery prepared in example 1-1The charge-discharge cycle curves below, where 1,2 and 3 represent the first, second and third cycles, respectively.
FIG. 4 shows the current density of the bismuth/carbon composite assembled sodium ion battery prepared in example 1 (from 100mA g)-1～5000mA·g-1) The rate performance graph of (1).
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
(1) Weighing 1g of triphenyl bismuth and 2.29g of terephthaloyl chloride (quickly weighed to prevent the terephthaloyl chloride from absorbing water in the air) according to the molar ratio of 1:5, placing the weighed materials in a mortar, and grinding and uniformly mixing the materials in the mortar; then, 2g of anhydrous ferric chloride is quickly weighed and added into the system, and the mixture is continuously ground and uniformly mixed to obtain a mixture;
(2) crosslinking and reacting the mixture ground and uniformly mixed in the step (1) in a constant-temperature drying oven at 70 ℃ for 12 hours, repeatedly performing suction filtration by using deionized water after the crosslinking reaction is completed, cleaning ferric trichloride, and drying the suction-filtered sample in a vacuum drying oven at 70 ℃ overnight to obtain dark green solid powder which is a crosslinked product;
(3) transferring the dark green solid powder prepared in the step (2) into a crucible, putting the crucible into a tubular furnace continuously filled with argon, and controlling the temperature at 5 ℃ for min-1The temperature rise rate is up to 800 ℃, and the temperature is kept for 2 hours, so that the bismuth/carbon composite material is obtained, wherein a thermogravimetric test shows that: the bismuth content in the bismuth/carbon composite material is 57 percent; FIG. 1 is an XRD pattern of the bismuth/carbon composite material, from which it can be seen thatThe diffraction peak of the XRD spectrogram is almost consistent with the spectrogram corresponding to the standard card Bi PDF #44-1246, which indicates that the material contains bismuth; the material purity is higher due to no obvious impurity peak; meanwhile, the spectrogram does not have a characteristic peak of a carbon material, which indicates that C in the bismuth/carbon composite material is amorphous carbon.
(4) Uniformly mixing and grinding the bismuth/carbon composite material prepared in the step (3), the conductive carbon black and PVDF according to the mass ratio of 8:1:1, and dropwise adding N-methyl pyrrolidone to uniformly mix to prepare slurry; then coating the bismuth/carbon composite material on copper foil, vacuum drying at 60 ℃ for 12h, and rolling to obtain a bismuth/carbon composite material electrode plate;
(5) punching the bismuth/carbon composite electrode slice prepared in the step (4)
Of wafers of
Metal sodium sheet as counter electrode, glass fiber as diaphragm, 1mol/L NaPF6the/DIG is electrolyte and is assembled into a button cell in a glove box filled with argon. A battery testing system (CT2001A) is adopted to test the battery, and the charging and discharging voltage range is 0.01-3V.
FIG. 2 shows the concentration of bismuth in the sodium ion battery at 1000mA g in the bismuth/carbon composite material fabricated in this example-1Current density of (c) cycle constant current charge-discharge diagram of 40 cycles. 1000mA g-1The first charge capacity of charge and discharge is 258mAh g-1The first discharge capacity is 330mAh g-1Compared with the first circulation, the specific capacity of the second circulation is obviously reduced, but after 40 circulations, the discharge capacity can still reach 232mAh g-1The capacity retention rate was 75%. Coulombic efficiency was 78% in the first cycle, but increased rapidly to 100.68% in the second cycle, and then remained stable around 102.2% in subsequent cycles, indicating that sodium storage is significantly reversible.
FIG. 3 is a view showing the bismuth/carbon composite material fabricated in the present exampleThe sodium ion battery is at 1000 mA.g-1The charge-discharge cycle curve chart in the figure corresponds to the oxidation-reduction reaction in the charge-discharge process. The second and third charge-discharge curves almost coincide again indicating that sodium storage is significantly reversible.
FIG. 4 shows the current density of the bismuth/carbon composite assembled Na-ion battery prepared in this example (from 100mA g)-1To 5000mA g-1) The rate performance graph of (1). When the current density is 100mA · g-1When the average reversible capacity is 288mAh g-1Even if the current density reaches 5000mA · g-1The capacity can be kept at 210mAh g-1When the current density is recovered to 100mA g-1When the capacity is increased to 275mAh g-1And remain stable over long cycles. This shows that the bismuth/carbon composite material prepared by the present embodiment has excellent rate capability.
Example 2
(1) In this example, the influence of different carbonization temperatures (600, 800, 1000, 1200, 1400, 1600 ℃) and carbonization times (2, 6, 12h) on the electrochemical performance of the material is examined, and the steps of preparing the bismuth/carbon composite material except the carbonization temperature and the carbonization time are the same as those in example 1;
(2) the preparation of the bismuth/carbon composite electrode sheet is the same as that of example 1;
(3) button cell assembly and performance testing were the same as in example 1;
the sodium ion battery assembled by the bismuth/carbon composite material prepared after carbonization treatment at different carbonization temperatures and carbonization times is 1000mA g-1The results of constant current charging and discharging at the current density of (a) are shown in Table 1.
TABLE 1 influence of carbonization temperature (600-1600 ℃) and carbonization time (2-12 h) on electrochemical performance of bismuth/carbon composite material
Example 3
(1) In this example, the influence of the molar ratio (1:2, 1:3, 1:10) of the aromatic bismuth source to the crosslinking agent on the electrochemical performance of the material was examined, and the steps for preparing the bismuth/carbon composite material except for the molar ratio of the aromatic bismuth source to the crosslinking agent were the same as in example 1;
(2) the preparation of the bismuth/carbon composite electrode sheet is the same as that of example 1;
(3) button cell assembly and performance testing were the same as in example 1;
the molar ratio of the aromatic bismuth source to the cross-linking agent is different, and the prepared bismuth/carbon composite material electrode slice is 1000mA g-1The results of constant current charging and discharging at the current density of (a) are shown in Table 2.
TABLE 2 influence of molar ratio of aromatic bismuth source to crosslinking agent (1: 2-1: 10) on electrochemical performance of bismuth/carbon composite material
Example 4
(1) In this example, the influence of the mass ratio of the aromatic bismuth source to the catalyst (1:0.5, 1:2, 1:5) on the electrochemical performance of the material was examined, and the steps for preparing the bismuth/carbon composite material except for the mass ratio of the aromatic bismuth source to the catalyst were the same as in example 1;
(2) the preparation of the bismuth/carbon composite electrode sheet is the same as that of example 1;
(3) button cell assembly and performance testing were the same as in example 1;
the electrode slice of the bismuth/carbon composite material prepared by different mass ratios of the aromatic bismuth source and the catalyst is 1000 mA.g-1The results of constant current charging and discharging at the current density of (a) are shown in Table 3.
TABLE 3 influence of the ratio of the aromatic bismuth source to the catalyst (1: 0.5-1: 5) on the electrochemical properties of bismuth/carbon composites
Example 5
(1) In the embodiment, the influence of the crosslinking temperature (60-100 ℃) and the crosslinking time (10-24 hours) on the electrochemical performance of the material is examined, and except for the crosslinking temperature and the crosslinking time, other steps for preparing the bismuth/carbon composite material are the same as those in the embodiment 1;
(2) the preparation of the bismuth/carbon composite electrode sheet is the same as that of example 1;
(3) button cell assembly and performance testing were the same as in example 1;
the bismuth/carbon composite electrode slice prepared at different crosslinking temperatures and crosslinking times is 1000 mA-g-1The results of constant current charging and discharging at the current density of (a) are shown in Table 4.
TABLE 4 influence of crosslinking temperature (60-100 ℃) and crosslinking time (10-24 h) on electrochemical performance of bismuth/carbon composite material
Example 6
(1) Weighing 1g of triphenyl bismuth and 0.86g of dimethoxymethane according to the molar ratio of 1:5, placing the triphenyl bismuth and the dimethoxymethane into a mortar, and grinding and mixing the triphenyl bismuth and the dimethoxymethane uniformly in the mortar; then, 2g of anhydrous aluminum chloride is quickly weighed and added into the system, and the mixture is continuously ground and uniformly mixed to obtain a mixture;
(2) carrying out crosslinking reaction on the mixture ground and uniformly mixed in the step (1) in a constant-temperature drying oven at 70 ℃ for 12 hours, repeatedly carrying out suction filtration by using hydrochloric acid with the mass fraction of 10% and deionized water after the crosslinking reaction is finished, cleaning aluminum trichloride, and drying a sample in a vacuum drying oven at 70 ℃ overnight after the suction filtration to obtain dark green solid powder, namely a crosslinked product;
(3) transferring the dark green solid powder prepared in the step (2) into a crucible, putting the crucible into a tubular furnace continuously filled with argon, and controlling the temperature at 5 ℃ for min-1Heating to 800 ℃ and keeping the temperature for 2 hours to obtain the bismuth/carbon composite material; wherein, the thermogravimetric test shows that: the bismuth content in the bismuth/carbon composite material is 68%, and when the bismuth/carbon composite material is used as a negative electrode material of a sodium ion battery, the initial discharge capacity is 371mAh g-1。
Example 7
(1) Weighing 1.26g of tri-o-tolyl bismuth dichloride and 2.31g of terephthaloyl chloride (quickly weighed to prevent the terephthaloyl chloride from absorbing water in the air) according to a molar ratio of 1:5, placing the weighed materials in a mortar, and grinding and uniformly mixing the materials in the mortar; then, 2g of anhydrous ferric chloride is quickly weighed and added into the system, and the mixture is continuously ground and uniformly mixed to obtain a mixture;
(2) carrying out crosslinking reaction on the mixture ground and uniformly mixed in the step (1) in a constant-temperature drying oven at 70 ℃ for 12h, repeatedly carrying out suction filtration by using hydrochloric acid with the mass fraction of 10% and deionized water after the crosslinking reaction is finished, cleaning ferric trichloride, and drying a sample in a vacuum drying oven at 70 ℃ overnight after the suction filtration to obtain dark green solid powder, namely a crosslinked product;
(3) transferring the dark green solid powder prepared in the step (2) into a crucible, putting the crucible into a tubular furnace continuously filled with argon, and controlling the temperature at 5 ℃ for min-1Heating to 800 ℃ and keeping the temperature for 2 hours to obtain the bismuth/carbon composite material; wherein, the thermogravimetric test shows that: the bismuth content in the bismuth/carbon composite material is 51 percent, and when the bismuth/carbon composite material is used as a negative electrode material of a sodium-ion battery, the first discharge capacity is 308 mAh.g-1。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The preparation method of the bismuth/carbon composite material is characterized by comprising the following steps:
(1) grinding and uniformly mixing an aromatic bismuth source and a cross-linking agent according to a molar ratio of (1:2) - (1:10), adding a catalyst, continuously grinding, and uniformly mixing to obtain a mixture;
(2) carrying out crosslinking reaction on the mixture ground and uniformly mixed in the step (1) at the temperature of 60-100 ℃ for 10-24 h, purifying and collecting a sample after the crosslinking reaction is finished, and drying to obtain a crosslinked product;
(3) and (3) carbonizing the cross-linked product prepared in the step (2) for 2-12 hours at 600-1600 ℃ in an inert gas atmosphere to obtain the bismuth/carbon composite material.
2. The method for preparing a bismuth/carbon composite material according to claim 1, wherein:
the aromatic bismuth source in the step (1) is at least one of triphenyl bismuth, tri-o-tolyl bismuth dichloride and other organic metal compounds containing aromatic rings and bismuth atoms.
3. The method for preparing a bismuth/carbon composite material according to claim 1, wherein:
the cross-linking agent in the step (1) is at least one of terephthaloyl chloride, phthaloyl chloride, carbon tetrachloride, dimethoxymethane, 1, 2-dichloroethane and p-dichlorobenzyl.
4. The method for preparing a bismuth/carbon composite material according to claim 1, wherein:
the catalyst in the step (1) is at least one of anhydrous aluminum trichloride, anhydrous ferric trichloride and anhydrous stannic chloride.
5. The method for preparing a bismuth/carbon composite material according to claim 1, wherein:
the mass ratio of the aromatic bismuth source to the catalyst in the step (1) is (1:0.5) - (1: 5).
6. The method for preparing a bismuth/carbon composite material according to claim 1, wherein:
and (3) the inert gas atmosphere in the step (3) is nitrogen or argon.
7. The method for preparing a bismuth/carbon composite material according to claim 1, wherein:
the carbonization treatment in the step (3) is carried out at a temperature of 5 ℃ min-1The temperature rise rate is 600-1600 ℃, and then the temperature is kept for 2-12 h.
8. A bismuth/carbon composite material characterized by being produced by the production method according to any one of claims 1 to 7.
9. Use of the bismuth/carbon composite material according to claim 8 in the field of sodium ion battery production.
10. A bismuth/carbon composite electrode sheet characterized by comprising the bismuth/carbon composite material according to claim 8.
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