CN117219758A - MXene composite material, preparation method and application thereof, and preparation method of sodium ion battery anode - Google Patents
MXene composite material, preparation method and application thereof, and preparation method of sodium ion battery anode Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 25
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 61
- 239000002028 Biomass Substances 0.000 claims abstract description 58
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 36
- 239000000725 suspension Substances 0.000 claims description 33
- 241000228245 Aspergillus niger Species 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 238000001354 calcination Methods 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 17
- 238000005530 etching Methods 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- MATGKVZWFZHCLI-LSDHHAIUSA-N (-)-matairesinol Chemical compound C1=C(O)C(OC)=CC(C[C@@H]2[C@H](C(=O)OC2)CC=2C=C(OC)C(O)=CC=2)=C1 MATGKVZWFZHCLI-LSDHHAIUSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001462 antimony Chemical class 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 claims description 3
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 238000009831 deintercalation Methods 0.000 abstract description 3
- 238000009830 intercalation Methods 0.000 abstract description 3
- 230000002687 intercalation Effects 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 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 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 43
- 239000010408 film Substances 0.000 description 26
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 239000012300 argon atmosphere Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 10
- 238000012258 culturing Methods 0.000 description 10
- 239000010453 quartz Substances 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000009210 therapy by ultrasound Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 230000002441 reversible effect Effects 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 241000233866 Fungi Species 0.000 description 7
- 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 description 7
- 239000001888 Peptone Substances 0.000 description 7
- 108010080698 Peptones Proteins 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000008103 glucose Substances 0.000 description 7
- 235000019319 peptone Nutrition 0.000 description 7
- 230000001954 sterilising effect Effects 0.000 description 7
- 238000004108 freeze drying Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000004506 ultrasonic cleaning Methods 0.000 description 5
- 238000011144 upstream manufacturing Methods 0.000 description 5
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
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Abstract
The invention belongs to the technical field of sodium ion batteries, and particularly relates to an MXene composite material, a preparation method and application thereof, and a preparation method of a negative electrode of a sodium ion battery. In the invention, the biomass-derived carbon can remarkably improve the conductivity of the material and is beneficial to electron and ion transmission. In the circulation process, the MXene and biomass derived carbon can relieve the volume expansion of metal sulfides, and simultaneously, the MXene can relieve the structure collapse caused by sodium intercalation and deintercalation, so that the circulation stability of the material is obviously improved; the MXene film with light weight and excellent conductivity and mechanical property is used as a current collector, and the one-dimensional metal sulfide modified biomass-derived carbon composite material effectively prevents the MXene from being stacked, so that electrolyte can be fully soaked, and sufficient space is provided for embedding and extracting sodium ions. The electrochemical performance of the sodium ion battery is improved through the combined action of the MXene and the modified biomass derived carbon.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to an MXene composite material, a preparation method and application thereof, and a preparation method of a negative electrode of a sodium ion battery.
Background
MXene is an emerging two-dimensional nanomaterial with high conductivity, abundant end groups, large specific surface area, and hydrophilicity. mXene-based composite electrode materials for energy storage have been widely studied. The rich terminal groups and unique lamellar structure make it a potential candidate for flexible electrodes. By utilizing the unique characteristics of the MXene, the MXene membrane electrode can be easily prepared by a vacuum filtration device. MXene films are considered promising current collectors because of their light weight, excellent electrical conductivity and mechanical properties.
However, due to strong van der Waals interactions and hydrogen bonds between adjacent few layers of MXene sheets, aggregation and dead weight accumulation are caused, the contact area of the electrolyte is seriously reduced, the accessibility of electrolyte ions and the full utilization of MXenes active sites are limited, and the electrochemical performance of the battery is further reduced.
Disclosure of Invention
The invention aims to provide an MXene composite material, a preparation method and application thereof, and a preparation method of a sodium ion battery cathode.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an MXene composite material, which comprises an MXene matrix and modified biomass-derived carbon positioned in a lamellar layer of the MXene matrix;
the modified biomass-derived carbon comprises a biochar carrier and a metal sulfide supported on the biochar carrier;
the chemical composition of the MXene matrix is Ti 3 C 2 T x 。
Preferably, the metal sulfide comprises tin sulfide and/or antimony sulfide;
the load mass percentage of the metal sulfide on the modified biomass derived carbon is 30-50%.
Preferably, the mass ratio of the MXene matrix to the modified biomass-derived carbon is 4:6.
the invention also provides a preparation method of the MXene composite material, which comprises the following steps:
ti is mixed with 3 AlC 2 Mixing MAX, lithium fluoride and hydrochloric acid solution, and etching to obtain Ti 3 C 2 T x MXene suspension;
mixing metal salt, aspergillus niger balls and ethanol, and carrying out shake culture to obtain a precursor;
performing first calcination on the precursor to obtain doped biochar;
mixing the doped biological carbon with a sulfur source, and performing second calcination to obtain modified biomass derived carbon;
deriving the carbon from the modified biomass and the Ti 3 C 2 T x The MXene suspension is mixed to obtain the MXene composite material.
Preferably, the Ti is 3 AlC 2 The mass ratio of MAX to lithium fluoride is 3:4.8;
the concentration of the hydrochloric acid solution is 9mol/L;
the dosage ratio of the lithium fluoride to the hydrochloric acid solution is 4.8g:60mL;
the etching temperature is 35 ℃ and the etching time is 48 hours.
Preferably, the metal salt comprises a tin salt and/or an antimony salt;
the mass ratio of the metal salt to the aspergillus niger balls is 13:1 or (21:1);
the dosage ratio of the metal salt to the ethanol is 13-21 g:300mL;
the temperature of the shaking culture is 35 ℃ and the time is 24 hours;
the temperature of the first calcination is 500-600 ℃, and the heat preservation time is 1-2 hours;
preferably, the sulfur source comprises thiourea and/or sublimed sulfur;
the mass ratio of the sulfur source to the doped biochar is 4:1, a step of;
the temperature of the second calcination is 400 ℃, and the heat preservation time is 2-4 hours.
Preferably, the Ti is 3 C 2 T x The concentration of the MXene suspension is 10mg/mL;
the modified biomass-derived carbon and the Ti 3 C 2 T x The dose ratio of the MXene suspension was 60mg:4mL;
the modified biomass-derived carbon and the Ti 3 C 2 T x The MXene suspension is mixed under stirring; the stirring time is 6-12 hours.
The invention also provides an application of the MXene composite material in the negative electrode of the sodium ion battery, which is prepared by the MXene composite material or the preparation method.
The invention also provides a preparation method of the sodium ion battery cathode, which comprises the following steps:
vacuum filtering the dispersion liquid containing the negative electrode material to form a film, and drying the obtained wet film to obtain the negative electrode of the sodium ion battery;
the negative electrode material is the MXene composite material prepared by the technical scheme or the preparation method.
The invention provides an MXene composite material, which comprises an MXene matrix and modified biomass-derived carbon positioned in a lamellar layer of the MXene matrix; the modified biomass-derived carbon comprises a biochar carrier and a metal sulfide supported on the biochar carrier; the chemical composition of the MXene matrix is Ti 3 C 2 T x . In the invention, the biomass-derived carbon can remarkably improve the conductivity of the material and is beneficial to electron and ion transmission. In the circulation process, MXene and biomass derived carbon can relieve the volume expansion of metal sulfides, and Mxene can relieve the structural collapse caused by sodium intercalation and deintercalation, so that the circulation stability of the material is obviously improved; MXene thin film with light weight and excellent conductivity and mechanical property as current collectorThe collector and the one-dimensional metal sulfide modified biomass-derived carbon composite material effectively prevent MXene from being stacked, so that electrolyte can be fully soaked, and sufficient space is provided for sodium ion intercalation and deintercalation. The electrochemical performance of the sodium ion battery is improved through the combined action of the MXene and the modified biomass derived carbon.
Drawings
FIG. 1 shows the Ti as obtained in example 1 3 C 2 T x XRD pattern of MXene film;
FIG. 2 shows the Ti as obtained in example 1 3 C 2 T x SEM cross-sectional view of MXene film;
FIG. 3 is an SEM image of biochar NCFs obtained in comparative example 1;
FIG. 4 shows XRD patterns of modified biomass-derived carbon obtained in examples 1-2, wherein pattern (a) is SnS obtained in example 1 2 @NCFs, (b) is Sb obtained in example 2 2 S 3 @NCFs；
FIG. 5 is an SEM image of the negative electrode obtained in examples 1-2, wherein (a) is MXene/SnS obtained in example 1 2 (b) MXene/Sb obtained in example 2 2 S 3 @NCFs；
FIG. 6 is a graph showing the cycle performance of the negative electrode obtained in comparative example 1, wherein (a) is a graph showing the cycle performance at a current density of 100mA/g, and (b) is a graph showing the cycle performance at a current density of 1A/g;
FIG. 7 shows the charge and discharge curves of the cathodes obtained in examples 1-2 at a current density of 100mA/g, wherein (a) is example 1 and (b) is example 2;
FIG. 8 is a graph showing the cycle performance of the negative electrode obtained in examples 1 to 2 at a current density of 100mA/g, wherein (a) is example 1 and (b) is example 2;
FIG. 9 is a graph showing the cycle performance of the negative electrode obtained in examples 1 to 2 at a current density of 1A/g, wherein (a) is example 1 and (b) is example 2;
FIG. 10 is a graph showing the ratio performance of the negative electrode obtained in examples 1-2 at different current densities, wherein (a) is example 1 and (b) is example 2;
FIG. 11 is a graph showing the cycle performance of the composite material obtained in comparative example 2;
FIG. 12 is a graph showing the cycle performance of the composite material obtained in comparative example 3.
Detailed Description
The invention provides an MXene composite material, which comprises an MXene matrix and modified biomass-derived carbon positioned in a lamellar layer of the MXene matrix;
the modified biomass-derived carbon comprises a biochar carrier and a metal sulfide supported on the biochar carrier;
the chemical composition of the MXene matrix is Ti 3 C 2 T x 。
In the present invention, the metal sulfide includes tin sulfide and/or antimony sulfide; the loading mass percentage of the metal sulfide on the modified biomass-derived carbon is preferably 30-50%, more preferably 35-45%, and even more preferably 40%.
In the present invention, the mass ratio of the MXene matrix and the modified biomass-derived carbon is preferably 4:6.
the invention also provides a preparation method of the MXene composite material, which comprises the following steps:
ti is mixed with 3 AlC 2 Mixing MAX, lithium fluoride and hydrochloric acid solution, and etching to obtain Ti 3 C 2 T x MXene suspension;
mixing metal salt, aspergillus niger balls and ethanol, and carrying out shake culture to obtain a precursor;
performing first calcination on the precursor to obtain doped biochar;
mixing the doped biological carbon with a sulfur source, and performing second calcination to obtain modified biomass derived carbon;
deriving the carbon from the modified biomass and the Ti 3 C 2 T x The MXene suspension is mixed to obtain the MXene composite material.
In the present invention, all the preparation materials are commercially available products well known to those skilled in the art unless specified otherwise.
The invention uses Ti 3 AlC 2 Mixing MAX, lithium fluoride and hydrochloric acid solution, and etching to obtain Ti 3 C 2 T x MXene suspension.
In the present invention, the Ti is 3 AlC 2 The mass ratio of MAX to lithium fluoride is preferably 3:4.8. in the present invention, the concentration of the hydrochloric acid solution is preferably 9mol/L; the dosage ratio of the lithium fluoride to the hydrochloric acid solution is preferably 4.8g:60mL.
In the present invention, the Ti is 3 AlC 2 The mixing process of MAX, lithium fluoride and hydrochloric acid solution is preferably as follows: dissolving lithium fluoride in hydrochloric acid solution, and adding Ti 3 AlC 2 MAX. In the present invention, the dissolution is performed under stirring, and the stirring time is preferably 1h.
In the invention, the etching temperature is preferably 35 ℃ and the etching time is preferably 48 hours; the etching is preferably performed under stirring.
After the etching, the method also preferably comprises the steps of placing the etched product in sulfuric acid solution, stirring and oscillating, and performing first centrifugation; placing the precipitate obtained by the first centrifugation into deionized water, and performing a second centrifugation to obtain a supernatant which is Ti 3 C 2 T x MXene suspension.
In the present invention, the concentration of the sulfuric acid solution is preferably 2mol/L; the dosage ratio of the product to the sulfuric acid solution is 2g:60mL; the stirring time is preferably 1h; the rotational speed of the first centrifuge is preferably 3500rpm. In the present invention, the Ti is 3 C 2 T x The concentration of the MXene suspension is preferably 10mg/mL.
The invention mixes metal salt, aspergillus niger and ethanol, and carries out shaking culture to obtain a precursor.
In the present invention, the aspergillus niger balls are preferably prepared; the preparation method of the aspergillus niger balls preferably comprises the following steps:
mixing glucose, peptone and deionized water, sterilizing at high temperature under sealed condition, and cooling to room temperature to obtain culture solution;
and adding the aspergillus niger spores into the culture solution, and culturing to obtain the aspergillus niger balls.
The invention is not particularly limited to the type of Aspergillus niger strain producing Aspergillus niger spores, and the Aspergillus niger strain conventional in the art can be adopted.
In the present invention, the dosage ratio of glucose, peptone and deionized water is preferably 10g:8g:500mL. In the present invention, the mixing is preferably performed under ultrasonic conditions. In the present invention, the temperature of the high temperature sterilization is preferably 121℃and the time is preferably 15 minutes. In the present invention, the temperature of the culture is preferably 35℃and the time is preferably 36 hours. After the culture, the invention also preferably comprises the steps of taking out the obtained bacterial balls and then washing the bacterial balls with ethanol.
In the present invention, the metal salt includes a tin salt and/or an antimony salt; the mass ratio of the metal salt to the aspergillus niger balls is preferably 10-21: 1, more preferably 13 to 20:1, a step of; the dosage ratio of the metal salt to the ethanol is 13-21 g:300mL. In the invention, the mixing process of the metal salt, the aspergillus niger balls and the ethanol is preferably as follows: after dissolving the metal salt in ethanol, adding Aspergillus niger balls.
In the present invention, the temperature of the shaking culture is preferably 35℃and the time is preferably 24 hours. After the shaking culture, the invention also preferably comprises the steps of sequentially cleaning and drying the obtained product; the cleaning is preferably performed by adopting ethanol; the drying is preferably freeze drying; the temperature of the freeze-drying is preferably-50 ℃; the cooling and drying time is preferably 1-2 d.
After the precursor is obtained, the precursor is subjected to first calcination to obtain the doped biochar.
In the invention, the temperature of the first calcination is preferably 500-600 ℃, and the heating rate from the temperature rise to the first calcination temperature is preferably 3 ℃/min; the heat preservation time is preferably 1-2 hours; the first calcination is preferably performed in an argon atmosphere.
After the doped biochar is obtained, the doped biochar and a sulfur source are mixed, and second calcination is carried out to obtain the modified biomass derived carbon.
In the present invention, the sulfur source preferably includes thiourea and/or sublimed sulfur; the mass ratio of the sulfur source to the doped biochar is preferably 4:1. in the invention, the temperature of the second calcination is preferably 400 ℃, and the heat preservation time is preferably 2-4 hours. In the present invention, the second calcination is preferably performed in an argon atmosphere; the second calcination is preferably carried out in a tube furnace.
In a specific embodiment of the present invention, the calcination process is preferably: placing the ceramic boat containing the doped biological carbon at the downstream of a quartz tube of a tube furnace, placing the ceramic boat containing a sulfur source at the upstream of the quartz tube, and calcining under argon flow.
After the modified biomass-derived carbon is obtained, the modified biomass-derived carbon and the Ti are treated by the method of the invention 3 C 2 T x The MXene suspension is mixed to obtain the MXene composite material.
In the present invention, the modified biomass-derived carbon and the Ti 3 C 2 T x The dose ratio of the MXene suspension was 60mg:4mL. In the present invention, the modified biomass-derived carbon is preferably added in the form of a modified biomass-derived carbon suspension; the preparation method of the modified biomass-derived carbon is preferably as follows: and mixing the modified biomass-derived carbon with deionized water, and performing ultrasonic treatment to obtain the modified biomass-derived carbon suspension. In the present invention, the dosage ratio of the modified biomass-derived carbon to deionized water is preferably 60mg:21mL; the time of the ultrasonic treatment is preferably 2 hours.
In the present invention, the modified biomass-derived carbon and the Ti 3 C 2 T x The mixing of the MXene suspension is preferably carried out under stirring; the stirring time is preferably 6-12 hours. After the mixing, the invention also preferably comprises the step of drying the obtained mixed liquor. The drying process is not particularly limited, and may be performed as known to those skilled in the art.
The invention also provides an application of the MXene composite material in the negative electrode of the sodium ion battery, which is prepared by the MXene composite material or the preparation method.
The invention also provides a preparation method of the sodium ion battery cathode, which comprises the following steps:
vacuum filtering the dispersion liquid containing the negative electrode material to form a film, and drying the obtained wet film to obtain the negative electrode of the sodium ion battery; the negative electrode material is the MXene composite material prepared by the technical scheme or the preparation method.
The process of vacuum filtration film formation is not particularly limited, and can be well known to those skilled in the art. In the present invention, the drying is preferably vacuum drying; the temperature of the vacuum drying is preferably 30 ℃, and the time is preferably 12-24 hours.
In the present invention, the thickness of the negative electrode of the sodium ion battery is preferably 10 μm.
For further explanation of the present invention, the following description will be given in detail of an MXene composite material, its preparation method and application, and a preparation method of a negative electrode of a sodium ion battery, which are provided by the present invention, with reference to the accompanying drawings and examples, but they are not to be construed as limiting the scope of the present invention.
Example 1
Adding 4.8g of lithium fluoride into 60mL of hydrochloric acid solution with the concentration of 9mol/L, and stirring for 1h to fully dissolve the lithium fluoride; slowly add 3g Ti 3 AlC 2 MAX is added into the solution and magnetically stirred for 48 hours at 35 ℃ to realize Ti 3 AlC 2 Etching MAX; placing the etched product into 60mL sulfuric acid solution with the concentration of 2mol/L, magnetically stirring for 1h, oscillating, and centrifuging at 3500 rpm; mixing the obtained precipitate with deionized water, and centrifuging to obtain Ti with concentration of 10mg/mL 3 C 2 Tx MXene suspension;
adding 10g glucose, 8g peptone and 500mL deionized water into a 500mL conical flask, performing ultrasonic treatment in an ultrasonic cleaning machine to obtain uniform culture solution, sealing with a sealing film, sterilizing at 121deg.C for 15min, and cooling to room temperature in an ultra clean bench; adding Aspergillus niger spores into the culture solution, and placing the conical flask in a shaking incubator at 35 ℃ for culturing for 36h; taking out the cultured fungus balls, and washing the culture solution with absolute ethyl alcohol to obtain Aspergillus niger fungus balls;
21g of SnCl 4 ·5H 2 Mixing O and 300mL absolute ethanol in an erlenmeyer flask; then adding 1g of Aspergillus niger balls, and culturing for 24 hours under shaking at 35 ℃; filtering the obtained product, washing the solution with ethanol, treating with liquid nitrogen, and freeze-drying at-50deg.C under vacuum to obtain precursor; heating the obtained precursor to 600 ℃ in an argon atmosphere at a heating rate of 3 ℃/min for calcination, and keeping the temperature for 2 hours to obtain doped biochar (marked as Sn@NCFs);
placing a ceramic boat containing 400mg of sulfur powder on the upstream of a quartz tube, placing a ceramic boat containing 100mg of doped biochar on the downstream of the quartz tube, and calcining at 400 ℃ for 2h in an argon atmosphere to obtain modified biomass-derived carbon (denoted as SnS 2 @NCFs）；
60mg of SnS 2 Adding @ NCFs into 21mL deionized water, and performing ultrasonic treatment for 2 hours to modify the biomass-derived carbon suspension; the resulting suspension was combined with 4mL of Ti 3 C 2 Mixing Tx MXene suspension, and stirring for 6h to obtain a uniform mixed solution; 3mL of the mixed solution was filtered under vacuum to obtain a wet film, and the obtained wet film was placed in a vacuum oven and dried under vacuum at 30℃for 24 hours to obtain a negative electrode (denoted as MXene/SnS) of a sodium ion battery having a thickness of 10. Mu.m 2 @NCFs, wherein SnS 2 Is 20% by weight).
Example 2
Adding 4.8g of lithium fluoride into 60mL of hydrochloric acid solution with the concentration of 9mol/L, and stirring for 1h to fully dissolve the lithium fluoride; slowly add 3g Ti 3 AlC 2 MAX is added into the solution and magnetically stirred for 48 hours at 35 ℃ to realize Ti 3 AlC 2 Etching MAX; placing the etched product into 60mL sulfuric acid solution with the concentration of 2mol/L, magnetically stirring for 1h, oscillating, and centrifuging at 3500 rpm; mixing the obtained precipitate with deionized water, and centrifuging to obtain Ti with concentration of 10mg/mL 3 C 2 Tx MXene suspension;
adding 10g glucose, 8g peptone and 500mL deionized water into a 500mL conical flask, performing ultrasonic treatment in an ultrasonic cleaning machine to obtain uniform culture solution, sealing with a sealing film, sterilizing at 121deg.C for 15min, and cooling to room temperature in an ultra clean bench; adding Aspergillus niger spores into the culture solution, and placing the conical flask in a shaking incubator at 35 ℃ for culturing for 36h; taking out the cultured fungus balls, and washing the culture solution with absolute ethyl alcohol to obtain Aspergillus niger fungus balls;
13g of SbCl 3 And 300mL of absolute ethanol in an erlenmeyer flask; then adding 1g of Aspergillus niger balls, and culturing for 24 hours under shaking at 35 ℃; filtering the obtained product, washing the solution with ethanol, treating with liquid nitrogen, and freeze-drying at-50deg.C under vacuum to obtain precursor; heating the obtained precursor to 600 ℃ in an argon atmosphere at a heating rate of 3 ℃/min for calcination, and keeping the temperature for 2 hours to obtain doped biochar (recorded as Sb@NCFs);
placing a ceramic boat containing 400mg of sulfur powder on the upstream of a quartz tube, placing a ceramic boat containing 100mg of doped biochar on the downstream of the quartz tube, and calcining at 400 ℃ for 2h in an argon atmosphere to obtain modified biomass-derived carbon (denoted as Sb 2 S 3 @NCFs）；
60mg of Sb 2 S 3 Adding @ NCFs into 21mL deionized water, and performing ultrasonic treatment for 2 hours to modify the biomass-derived carbon suspension; the resulting suspension was combined with 4mL of Ti 3 C 2 Mixing Tx MXene suspension, and stirring for 6h to obtain a uniform mixed solution; 3mL of the mixed solution was filtered under vacuum to obtain a wet film, and the obtained wet film was placed in a vacuum oven and dried under vacuum at 30℃for 24 hours to obtain a negative electrode (designated as MXene/Sb) of a sodium ion battery having a thickness of 10. Mu.m 2 S 3 @NCFs wherein Sb 2 S 3 Is 31% wt).
Comparative example 1
Adding 4.8g of lithium fluoride into 60mL of hydrochloric acid solution with the concentration of 9mol/L, and stirring for 1h to fully dissolve the lithium fluoride; slowly add 3g Ti 3 AlC 2 MAX is added into the solution and magnetically stirred for 48 hours at 35 ℃ to realize Ti 3 AlC 2 Etching MAX; the etched product was placed in 60mL of sulfuric acid solution with a concentration of 2mol/L,magnetically stirring for 1h, oscillating, and centrifuging at 3500 rpm; mixing the obtained precipitate with deionized water, and centrifuging to obtain Ti with concentration of 10mg/mL 3 C 2 Tx MXene suspension;
adding 10g glucose, 8g peptone and 500mL deionized water into a 500mL conical flask, performing ultrasonic treatment in an ultrasonic cleaning machine to obtain uniform culture solution, sealing with a sealing film, sterilizing at 121deg.C for 15min, and cooling to room temperature in an ultra clean bench; adding Aspergillus niger spores into the culture solution, and placing the conical flask in a shaking incubator at 35 ℃ for culturing for 36h; taking out the cultured fungus balls, washing the culture solution with absolute ethyl alcohol, treating the fungus balls with liquid nitrogen, and freeze-drying the fungus balls at the temperature of minus 50 ℃ in vacuum to obtain Aspergillus niger fungus balls; calcining the obtained Aspergillus niger balls in argon atmosphere at the temperature rising rate of 3 ℃/min to 600 ℃ for 2 hours to obtain biochar (recorded as NCFs);
adding 60mg of biochar into 21mL of deionized water, and carrying out ultrasonic treatment for 2 hours to modify the biomass-derived carbon suspension; the resulting suspension was combined with 4mL of Ti 3 C 2 Mixing Tx MXene suspension, and stirring for 6h to obtain a uniform mixed solution; 3mL of the mixed solution was filtered under vacuum to obtain a wet film, and the obtained wet film was placed in a vacuum oven and dried under vacuum at 30℃for 24 hours to obtain a negative electrode (denoted as MXene@NCFs) of a sodium ion battery having a thickness of 10. Mu.m.
Comparative example 2
Adding 10g glucose, 8g peptone and 500mL deionized water into a 500mL conical flask, performing ultrasonic treatment in an ultrasonic cleaning machine to obtain uniform culture solution, sealing with a sealing film, sterilizing at 121deg.C for 15min, and cooling to room temperature in an ultra clean bench; adding Aspergillus niger spores into the culture solution, and placing the conical flask in a shaking incubator at 35 ℃ for culturing for 36h; taking out the cultured fungus balls, and washing the culture solution with absolute ethyl alcohol to obtain Aspergillus niger fungus balls;
21g of SnCl 4 ·5H 2 Mixing O and 300mL absolute ethanol in an erlenmeyer flask; then adding 1g of Aspergillus niger balls, and culturing for 24 hours under shaking at 35 ℃; the obtained product was filtered off, the solution was washed with ethanol, treated with liquid nitrogen and lyophilized at-50℃under vacuumObtaining a precursor; heating the obtained precursor to 600 ℃ in an argon atmosphere at a heating rate of 3 ℃/min for calcination, and keeping the temperature for 2 hours to obtain doped biochar (marked as Sn@NCFs);
placing a ceramic boat containing 400mg of sulfur powder on the upstream of a quartz tube, placing a ceramic boat containing 100mg of doped biochar on the downstream of the quartz tube, and calcining at 400 ℃ for 2h in an argon atmosphere to obtain modified biomass-derived carbon (denoted as SnS 2 @NCFs, wherein SnS 2 The content of (3% by weight).
Comparative example 3
Adding 10g glucose, 8g peptone and 500mL deionized water into a 500mL conical flask, performing ultrasonic treatment in an ultrasonic cleaning machine to obtain uniform culture solution, sealing with a sealing film, sterilizing at 121deg.C for 15min, and cooling to room temperature in an ultra clean bench; adding Aspergillus niger spores into the culture solution, and placing the conical flask in a shaking incubator at 35 ℃ for culturing for 36h; taking out the cultured fungus balls, and washing the culture solution with absolute ethyl alcohol to obtain Aspergillus niger fungus balls;
13g of SbCl 3 And 300mL of absolute ethanol in an erlenmeyer flask; then adding 1g of Aspergillus niger balls, and culturing for 24 hours under shaking at 35 ℃; filtering the obtained product, washing the solution with ethanol, treating with liquid nitrogen, and freeze-drying at-50deg.C under vacuum to obtain precursor; heating the obtained precursor to 600 ℃ in an argon atmosphere at a heating rate of 3 ℃/min for calcination, and keeping the temperature for 2 hours to obtain doped biochar (recorded as Sb@NCFs);
placing a ceramic boat containing 400mg of sulfur powder on the upstream of a quartz tube, placing a ceramic boat containing 100mg of doped biochar on the downstream of the quartz tube, and calcining at 400 ℃ for 2h in an argon atmosphere to obtain modified biomass-derived carbon (denoted as Sb 2 S 3 @NCFs wherein Sb 2 S 3 The content of (3% by weight).
Performance testing
Test example 1
Ti obtained in example 1 3 C 2 Vacuum filtering the Tx MXene suspension to form a film to obtain Ti 3 C 2 Tx MXene film, FIG. 1 is Ti 3 C 2 T x XRD pattern of MXene film; FIG. 2 is Ti 3 C 2 T x As can be seen from FIGS. 1 to 2, the SEM cross section of the MXene film shows Ti 3 C 2 T x MXene has been successfully synthesized and has a tightly laminated structure.
Fig. 3 is an SEM image of the biochar NCFs obtained in comparative example 1, and it can be seen from fig. 3 that the biochar has a one-dimensional fibrous structure.
FIG. 4 is an XRD pattern of modified biomass-derived carbon obtained in example 1 and example 2, wherein pattern (a) is SnS obtained in example 1 2 @NCFs, (b) is Sb obtained in example 2 2 S 3 @NCFs, snS in modified biomass-derived carbons can be seen from FIG. 4 2 And Sb (Sb) 2 S 3 Is successfully synthesized and has good crystallinity.
FIG. 5 is an SEM image of the negative electrodes obtained in examples 1 and 2, wherein (a) is MXene/SnS obtained in example 1 2 (b) MXene/Sb obtained in example 2 2 S 3 From fig. 5 it can be seen that NCFs, showing the cross-sectional morphology of the flexible anode film, it can be clearly observed that the modified biomass-derived carbon is sandwiched in the layer by MXene sheets, and the anode film exhibits more pores, which can promote permeation of electrolyte, contributing to stable formation of SEI film during cycling.
Test example 2
Testing the electrochemical properties of the cathodes obtained in examples 1-2 and comparative example 1 and the composite materials obtained in comparative examples 2-3;
for the composite material obtained in comparative examples 2-3, the negative electrode prepared by the following method: mixing and grinding the composite material and acetylene black uniformly, dissolving a binder (PVDF) in an organic solvent, and then adding the uniformly ground mixture into the organic solvent dissolved with the binder, and stirring uniformly to prepare slurry (wherein the mass ratio of the composite material to the acetylene black to the PVDF is 7:2:1). Uniformly coating the slurry on the surface of a commercial copper foil, coating the slurry on the surface of the commercial copper foil with the thickness of 120 micrometers, and vacuum drying at 80 ℃ to prepare an electrode slice;
in a glove box filled with argon, sodiumThe sheet is a counter electrode, glass fiber (GF-D) is used as a separator, and EC: 1M NaClO in DEC (1:1 by volume, 5% FEC added) 4 The electrolyte is assembled into a button cell, and electrochemical performance of the obtained button cell is tested;
FIG. 6 is a graph of the cycle performance of the negative electrode obtained in comparative example 1, wherein (a) is a graph of the cycle performance at a current density of 100mA/g, and (b) is a graph of the cycle performance at a current density of 1A/g, and it can be seen from FIG. 6 that biomass-derived carbon has good stability at various current densities, but has a reversible specific capacity of only 125mAh/g after being cycled for 100 cycles at a current density of 100 mA/g;
FIG. 7 shows the charge and discharge curves of the cathodes obtained in examples 1-2 at a current density of 100mA/g, wherein (a) is example 1 and (b) is example 2; from fig. 7, it can be seen that examples 1-2 all have more obvious charge-discharge platforms of alloy-based metal sulfides.
FIG. 8 is a graph showing the cycle performance of the negative electrode obtained in examples 1 to 2 at a current density of 100mA/g, wherein (a) is example 1 and (b) is example 2; from fig. 8, it can be seen that examples 1 to 2 each have a high reversible specific capacity and excellent cycle stability. Example 1 can reach a specific discharge capacity of 739mAh/g at a current density of 100mA/g for the first cycle, and the specific discharge capacity of 592mAh/g is still maintained after 100 cycles; example 2 the first turn at a current density of 100mA/g can reach a specific discharge capacity of 648mAh/g, which remains 577mAh/g after 100 cycles.
FIG. 9 is a graph showing the cycle performance of the negative electrode obtained in examples 1 to 2 at a current density of 1A/g, wherein (a) is example 1 and (b) is example 2; it can be seen from fig. 9 that examples 1 to 2 all have excellent cycle stability and long cycle life in the cycle test at a large current density. Examples 1-2 had high reversible specific capacities of 592 and 395mAh/g, respectively, after 1000 cycles at a current density of 1A/g.
FIG. 10 is a graph showing the ratio performance of the negative electrode obtained in examples 1-2 at different current densities, wherein (a) is example 1 and (b) is example 2; from fig. 10, it can be seen that examples 1-2 all have higher reversible specific capacity and good cycle stability at different current densities. In particular, example 1 still has a high reversible specific capacity of about 347mAh/g at a current density of 20A/g.
FIG. 11 is a graph showing the cycle performance of the composite material obtained in comparative example 2, in which (a) is a graph showing the cycle performance at a current density of 100mA/g and (b) is a graph showing the cycle performance at a current density of 1A/g, as can be seen from FIG. 11 2 The modified biomass-derived carbon has higher initial specific capacity, but the cyclic stability is seriously insufficient, and the reversible specific capacity of the modified biomass-derived carbon is only 120mAh/g after 100 circles of circulation at the current density of 100 mA/g. The reversible specific capacity of the material is only 47mAh/g after 1000 cycles at a current density of 1A/g
FIG. 12 is a graph showing the cycle performance of the composite material obtained in comparative example 3, in which (a) is a graph showing the cycle performance at a current density of 100mA/g and (b) is a graph showing the cycle performance at a current density of 1A/g, as can be seen from FIG. 11, sb 2 S 3 The modified biomass-derived carbon has a higher initial specific capacity at a current density of 100mA/g, but has poor cycling stability, and only a reversible specific capacity of 312mAh/g after 100 cycles. The reversible specific capacity of the alloy is only 264mAh/g after 1000 cycles at a current density of 1A/g
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (10)
1. An MXene composite comprising an MXene matrix and a modified biomass-derived carbon in a platelet of the MXene matrix;
the modified biomass-derived carbon comprises a biochar carrier and a metal sulfide supported on the biochar carrier;
the chemical composition of the MXene matrix is Ti 3 C 2 T x 。
2. The MXene composite of claim 1, wherein the metal sulfide comprises tin sulfide and/or antimony sulfide;
the load mass percentage of the metal sulfide on the modified biomass derived carbon is 30-50%.
3. The MXene composite of claim 1, wherein the mass ratio of MXene matrix and modified biomass-derived carbon is 4:6.
4. a method for producing an MXene composite material according to any one of claims 1 to 3, characterized by comprising the steps of:
ti is mixed with 3 AlC 2 Mixing MAX, lithium fluoride and hydrochloric acid solution, and etching to obtain Ti 3 C 2 T x MXene suspension;
mixing metal salt, aspergillus niger balls and ethanol, and carrying out shake culture to obtain a precursor;
performing first calcination on the precursor to obtain doped biochar;
mixing the doped biological carbon with a sulfur source, and performing second calcination to obtain modified biomass derived carbon;
deriving the carbon from the modified biomass and the Ti 3 C 2 T x The MXene suspension is mixed to obtain the MXene composite material.
5. The method according to claim 4, wherein the Ti is 3 AlC 2 The mass ratio of MAX to lithium fluoride is 3:4.8;
the concentration of the hydrochloric acid solution is 9mol/L;
the dosage ratio of the lithium fluoride to the hydrochloric acid solution is 4.8g:60mL;
the etching temperature is 35 ℃ and the etching time is 48 hours.
6. The method according to claim 4, wherein the metal salt comprises a tin salt and/or an antimony salt;
the mass ratio of the metal salt to the aspergillus niger balls is 10-21: 1, a step of;
the dosage ratio of the metal salt to the ethanol is 13-21 g:300mL;
the temperature of the shaking culture is 35 ℃ and the time is 24 hours;
the temperature of the first calcination is 500-600 ℃, and the heat preservation time is 1-2 h.
7. The method of claim 4, wherein the sulfur source comprises thiourea and/or sublimed sulfur;
the mass ratio of the sulfur source to the doped biochar is 4:1, a step of;
the temperature of the second calcination is 400 ℃, and the heat preservation time is 2-4 hours.
8. The method according to claim 4, wherein the Ti is 3 C 2 T x The concentration of the MXene suspension is 10mg/mL;
the modified biomass-derived carbon and the Ti 3 C 2 T x The dose ratio of the MXene suspension was 60mg:4mL;
the modified biomass-derived carbon and the Ti 3 C 2 T x The MXene suspension is mixed under stirring; the stirring time is 6-12 hours.
9. Use of the MXene composite material according to any one of claims 1 to 4 or the MXene composite material prepared by the preparation method according to any one of claims 5 to 8 in a negative electrode of a sodium ion battery.
10. The preparation method of the sodium ion battery cathode is characterized by comprising the following steps:
vacuum filtering the dispersion liquid containing the negative electrode material to form a film, and drying the obtained wet film to obtain the negative electrode of the sodium ion battery;
the negative electrode material is the MXene composite material as claimed in any one of claims 1 to 4 or the MXene composite material prepared by the preparation method as claimed in any one of claims 5 to 8.
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| CN111554891A (en) * | 2020-04-24 | 2020-08-18 | 天津大学 | Method for preparing lithium-sulfur battery cathode material from three-dimensional mesoporous biochar |
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| CN108987674A (en) * | 2018-07-25 | 2018-12-11 | 山东大学 | A kind of flexibility MXene self-supported membrane/metallic composite and preparation method thereof, application |
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