CN117712322A - Tin bismuth-carbon composite material and preparation method and application thereof - Google Patents
Tin bismuth-carbon composite material and preparation method and application thereof Download PDFInfo
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- CN117712322A CN117712322A CN202311727355.6A CN202311727355A CN117712322A CN 117712322 A CN117712322 A CN 117712322A CN 202311727355 A CN202311727355 A CN 202311727355A CN 117712322 A CN117712322 A CN 117712322A
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- bismuth
- tin
- salt
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- 239000002131 composite material Substances 0.000 title claims abstract description 47
- -1 Tin bismuth-carbon Chemical compound 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 150000001621 bismuth Chemical class 0.000 claims abstract description 24
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 18
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000001694 spray drying Methods 0.000 claims abstract description 16
- 239000006230 acetylene black Substances 0.000 claims abstract description 15
- 238000003763 carbonization Methods 0.000 claims abstract description 13
- 239000011344 liquid material Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 5
- HMYNUKPKYAKNHH-UHFFFAOYSA-N acetylene;hydrate Chemical compound O.C#C HMYNUKPKYAKNHH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 238000005507 spraying Methods 0.000 claims description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 239000005011 phenolic resin Substances 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 6
- 238000000889 atomisation Methods 0.000 claims description 6
- 229910001414 potassium ion Inorganic materials 0.000 claims description 6
- 229910001415 sodium ion Inorganic materials 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 3
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 3
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 claims description 3
- JYIZNFVTKLARKT-UHFFFAOYSA-N phenol;1,3,5-triazine-2,4,6-triamine Chemical compound OC1=CC=CC=C1.NC1=NC(N)=NC(N)=N1 JYIZNFVTKLARKT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 abstract description 21
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052718 tin Inorganic materials 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 13
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 238000004220 aggregation Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 229910001451 bismuth ion Inorganic materials 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 229910001432 tin ion Inorganic materials 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 14
- 239000007773 negative electrode material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910018733 Sn—Bi—C Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- OLDOGSBTACEZFS-UHFFFAOYSA-N [C].[Bi] Chemical compound [C].[Bi] OLDOGSBTACEZFS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a tin bismuth-carbon composite material, a preparation method and application thereof, and belongs to the technical field of battery materials. The method comprises the steps of mixing a nitrogen-containing carbon source and dimethyl sulfoxide under a heating condition, gelatinizing, and adding bismuth salt and tin salt into the obtained sol to obtain a gel precursor; and mixing the gel precursor, the surfactant, the acetylene black and water, and then carrying out spray drying on the obtained liquid material in nitrogen or argon atmosphere to obtain the tin-bismuth-carbon composite material. According to the invention, a sol-gel method is adopted to compound a nitrogen-containing carbon source with bismuth and tin, bismuth element and tin element are uniformly dispersed in a carbon matrix, then powder is dispersed through spray drying to form precursor nano particles, aggregation of bismuth and tin metal is prevented, bismuth ions are reduced into bismuth simple substances through a carbonization process, meanwhile, tin ions are reduced into tin simple substances, and meanwhile, the combination of tin and bismuth is realized, so that the maximum energy storage characteristic of bismuth and tin is exerted, and the material has excellent electrochemical performance.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a tin bismuth-carbon composite material and a preparation method and application thereof.
Background
With the rapid development of portable electronic devices and smart grids, there is an increasing demand for power density and energy density, and thus a secondary battery having high capacity, small size, and light weight is urgently needed. However, conventional secondary batteries, such as lead-acid batteries, nickel-cadmium batteries, nickel-hydrogen batteries, and the like, have been severely limited in development due to factors such as size and weight. Therefore, lithium ion batteries having excellent characteristics such as high specific energy, light weight, long life, and the like have become a research hotspot. In addition, the current society's demand for large-scale, environmentally friendly, safe electrochemical energy storage devices is also increasing, but the relatively scarce lithium resources limit the further large-scale application of lithium ion batteries. Sodium ion batteries and potassium ion batteries have received extensive attention in recent years in academia and business due to their low cost and abundant resources. However, the current cathode material is limited by poor electrochemical performance, and the commercialization popularization of the cathode material is slow. Therefore, development of a high-performance anode material is imperative.
Alloy type negative electrode materials are very promising candidate materials due to their suitable redox reaction potential and higher energy density. Among them, bismuth (Bi) as a typical alloy type negative electrode material has been widely focused because of its advantages of higher theoretical capacity, larger interlayer spacing, relatively higher conductivity, and the like, as a representative negative electrode material, showing great potential for application. However, the huge volume expansion (409%) thereof causes collapse and severe pulverization of the electrode material structure during alloying/dealloying, thereby causing problems of rapid capacity fade, short cycle life and poor rate performance.
In order to solve the problems, the current common method is to compound bismuth and carbon-based materials so as to improve the conductivity, buffer the volume expansion in the charge and discharge process and improve the rate capability and the cycle stability of the battery. Therefore, it is of great importance to study new bismuth-based battery materials to accommodate large-scale commercial applications.
Disclosure of Invention
The invention aims to provide a tin bismuth-carbon composite material, a preparation method and application thereof, and the prepared tin bismuth-carbon composite material has excellent rate capability and cycle stability.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a tin bismuth-carbon composite material, which comprises the following steps:
mixing a nitrogen-containing carbon source and dimethyl sulfoxide under a heating condition, gelatinizing, and adding bismuth salt and tin salt into the obtained sol to obtain a gel precursor;
and mixing the gel precursor, the surfactant, the acetylene black and water, spray-drying the obtained liquid material, and carbonizing the liquid material in nitrogen or argon atmosphere to obtain the tin-bismuth-carbon composite material.
Preferably, the nitrogen-containing carbon source comprises one or more of polyacrylonitrile, polyaniline, polyimide, melamine phenolic resin, dicyandiamide phenolic resin and polyurethane; the heating temperature is 90-100 ℃.
Preferably, the bismuth salt comprises one or more of bismuth sulfate, bismuth nitrate pentahydrate, bismuth chloride and bismuth acetate; the tin salt comprises tin chloride pentahydrate; the mass ratio of the bismuth salt to the tin salt is 1:1-2.
Preferably, the mass ratio of the bismuth salt to the nitrogen-containing carbon source is 1:1-3.
Preferably, the surfactant comprises one or more of cetyltrimethylammonium bromide, sodium dodecyl sulfate and polyvinylpyrrolidone; the mass ratio of the bismuth salt to the surfactant is 0.2-0.5:0.2-0.5.
Preferably, the mass of the acetylene black is 5-10% of the total mass of the bismuth salt, the tin salt and the nitrogen-containing carbon source.
Preferably, the temperature of the spray drying is 150-200 ℃, the spraying quantity through a spraying system is 5-30 mL/min, and the atomization pressure is 5-40 MPa.
Preferably, the carbonization treatment is carried out at a temperature of 800-1200 ℃ for 2-5 hours.
The invention provides the tin bismuth-carbon composite material prepared by the preparation method.
The invention provides application of the tin-bismuth-carbon composite material in lithium ion batteries, sodium ion batteries or potassium ion batteries.
Compared with the prior art, the invention has the following beneficial effects:
the invention firstly adopts a sol-gel method to compound a nitrogen-containing carbon source with Bi and Sn, uniformly disperses bismuth element and tin element in a carbon matrix, then disperses powder in a spray drying process to form precursor nano particles, prevents aggregation of bismuth and tin metal, reduces bismuth ions into bismuth simple substance in a carbonization process, reduces tin ions into tin simple substance, and simultaneously realizes the combination of tin and bismuth, thereby exerting the maximum energy storage property of bismuth and tin. In addition, powder dispersion uniformity can be realized through spray drying, so that metal elements bismuth and tin are uniformly coated on a carbon matrix, thereby playing a good role in buffering the volume expansion of metal in the charge and discharge process, improving the conductivity of the metal, and improving the synergistic effect between bismuth, tin and carbon, so that the material has excellent electrochemical performance.
The method has the advantages of simple operation, short reaction time, no need of complicated and long-time hydrothermal reaction, high yield, easy control of the process, low energy consumption, good repeatability and suitability for large-scale commercial production. When the prepared composite material is used as a negative electrode material of a lithium, sodium and potassium ion battery, the composite material can show good electrochemical performance, such as long cycle life, high reversible capacity, fast charge and discharge rate and the like, and has wide application prospect in the field of secondary battery negative electrode materials.
Drawings
FIG. 1 is an SEM image of a tin bismuth-carbon composite material prepared according to example 1;
FIG. 2 is an EDS diagram of the tin bismuth-carbon composite material prepared in example 1;
FIG. 3 is a TEM image of the tin bismuth-carbon composite material prepared in example 1;
FIG. 4 is a cyclic voltammogram of the tin bismuth-carbon composite material prepared in example 1;
FIG. 5 is a graph showing the first charge and discharge of the Sn-Bi-C composite material prepared in example 1;
fig. 6 is a cycle life test chart of the tin bismuth-carbon composite material prepared in example 1.
Detailed Description
The invention provides a preparation method of a tin bismuth-carbon composite material, which comprises the following steps:
mixing a nitrogen-containing carbon source and dimethyl sulfoxide under a heating condition, gelatinizing, and adding bismuth salt and tin salt into the obtained sol to obtain a gel precursor;
and mixing the gel precursor, the surfactant, the acetylene black and water, spray-drying the obtained liquid material, and carbonizing the liquid material in nitrogen or argon atmosphere to obtain the tin-bismuth-carbon composite material.
The invention mixes the nitrogen-containing carbon source and dimethyl sulfoxide under the heating condition, and gelatinates, and adds bismuth salt and tin salt into the obtained sol to obtain gel precursor.
In the present invention, the nitrogen-containing carbon source preferably includes one or more of polyacrylonitrile, polyaniline, polyimide, melamine phenol resin, dicyandiamide phenol resin, and polyurethane; when the number of the nitrogen-containing carbon sources is two or more, the proportion of the nitrogen-containing carbon sources of different types is not particularly limited, and the nitrogen-containing carbon sources can be adjusted according to actual requirements.
The dosage of the dimethyl sulfoxide is not particularly limited, and the dimethyl sulfoxide can be adjusted according to actual requirements to ensure that materials are uniformly mixed to form gel.
In the present invention, the temperature of the heating is preferably 90 to 100 ℃, more preferably 95 ℃; the heating is preferably performed under oil bath + agitation conditions; the heating time is not particularly limited, and the material is ensured to be fully and uniformly mixed to form sol.
The invention preferably cools the sol to room temperature, then adds bismuth salt and tin salt, and uniformly stirs and mixes to obtain the gel precursor.
In the present invention, the bismuth salt preferably includes one or more of bismuth sulfate, bismuth nitrate pentahydrate, bismuth chloride and bismuth acetate; the tin salt preferably comprises tin chloride pentahydrate; the mass ratio of the bismuth salt to the tin salt is preferably 1:1-2, more preferably 1:1.5-1.8. When the bismuth salt is more than two of the above, the proportion of the bismuth salts of different types is not particularly limited, and the bismuth salts can be adjusted according to actual requirements.
In the present invention, the mass ratio of the bismuth salt to the nitrogen-containing carbon source is preferably 1:1 to 3, more preferably 1:1.5 to 2.
After the gel precursor is obtained, the gel precursor, the surfactant, the acetylene black and water are mixed, the obtained liquid material is spray-dried, and carbonization treatment is carried out in nitrogen or argon atmosphere, so that the tin-bismuth-carbon composite material is obtained.
In the present invention, the surfactant preferably includes one or more of cetyltrimethylammonium bromide, sodium dodecyl sulfate and polyvinylpyrrolidone; when the surfactant is more than two of the above, the proportion of the surfactants of different types is not particularly limited, and the surfactant can be adjusted according to actual requirements.
In the present invention, the mass ratio of the bismuth salt to the surfactant is preferably 0.2 to 0.5:0.2 to 0.5, more preferably 0.3 to 0.4:0.3 to 0.4.
In the present invention, the mass of the acetylene black is preferably 5 to 10% of the total mass of the bismuth salt, the tin salt and the nitrogen-containing carbon source, and more preferably 6 to 8%. According to the invention, the electronic conductivity of the final product can be improved by adopting the acetylene black, a high-speed conductive network in the product particles is constructed, and the charge and discharge rate and the cycling stability of the material are improved.
The water consumption is not particularly limited, and the water consumption can be adjusted according to actual requirements.
In the invention, the gel precursor, the surfactant, the acetylene black and the water are mixed preferably under the stirring condition of 30-50 ℃; the invention has no special limitation on the mixing time, and can ensure that the materials are fully and uniformly dispersed.
In the invention, the temperature of the spray drying is preferably 150-200 ℃, more preferably 160-180 ℃, and the spraying amount through a spraying system is preferably 5-30 mL/min, more preferably 10-20 mL/min; the atomization pressure is preferably 5 to 40MPa, more preferably 10 to 30MPa, and still more preferably 15 to 20MPa.
In the present invention, the temperature of the carbonization treatment is preferably 800 to 1200 ℃, more preferably 900 to 1100 ℃, and the time is preferably 2 to 5 hours, more preferably 3 to 4 hours.
And after the carbonization treatment is completed, obtaining the tin-bismuth-carbon composite material.
The invention provides the tin bismuth-carbon composite material prepared by the preparation method.
The invention provides application of the tin-bismuth-carbon composite material in lithium ion batteries, sodium ion batteries or potassium ion batteries. The method of application of the present invention is not particularly limited, and may be applied according to methods well known in the art.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
1g of nitrogen-containing carbon source is treatedPolyacrylonitrile) and 10mL of dimethyl sulfoxide were mixed under stirring at 90℃in an oil bath, gelled, cooled to room temperature, and 1.5g of Bi (NO) was added to the resulting sol 3 ) 3 ·5H 2 O and 1.5g SnCl 4 ·5H 2 O, stirring and mixing uniformly to obtain a gel precursor;
mixing the gel precursor, 1.5g of surfactant (cetyl trimethyl ammonium bromide), 0.2g of acetylene black and 100mL of deionized water under the stirring condition of 35 ℃, performing spray drying on the obtained liquid material, wherein the spray drying temperature is 150 ℃, the spraying quantity through a spray system is 20mL/min, the atomization pressure is 20MPa, placing the obtained product into a tubular furnace, and performing carbonization treatment in a nitrogen atmosphere, wherein the carbonization treatment temperature is 1000 ℃ and the time is 3h, thus obtaining the tin bismuth-carbon composite material.
Example 2
1g of a nitrogen-containing carbon source (melamine) and 10mL of dimethyl sulfoxide were mixed under stirring in an oil bath at 95℃to gel, and after cooling to room temperature, 1.5g of Bi (NO) was added to the resulting sol 3 ) 3 ·5H 2 O and 2g SnCl 4 ·5H 2 O, stirring and mixing uniformly to obtain a gel precursor;
mixing the gel precursor, 3g of surfactant (sodium dodecyl sulfonate), 0.3g of acetylene black and 100mL of deionized water under the stirring condition of 50 ℃, spray-drying the obtained liquid material, wherein the spray-drying temperature is 200 ℃, the spraying quantity through a spray system is 30mL/min, the atomization pressure is 40MPa, placing the obtained product into a tube furnace, and performing carbonization treatment in a nitrogen atmosphere, wherein the carbonization treatment temperature is 800 ℃ and the time is 5h, thus obtaining the tin bismuth-carbon composite material.
Example 3
1g of a nitrogen-containing carbon source (dicyandiamide phenol resin) and 10mL of dimethyl sulfoxide were mixed under stirring in an oil bath at 100℃to gel, and after cooling to room temperature, 1.5. 1.5gBi (NO) was added to the resulting sol 3 ) 3 ·5H 2 O and 1.5g SnCl 4 ·5H 2 O, stirring and mixing uniformly to obtain a gel precursor;
mixing the gel precursor, 1.5g of surfactant (polyvinylpyrrolidone), 0.4g of acetylene black and 100mL of deionized water under the stirring condition of 30 ℃, performing spray drying on the obtained liquid material, wherein the spray drying temperature is 180 ℃, the spraying quantity through a spray system is 10mL/min, the atomization pressure is 10MPa, placing the obtained product into a tube furnace, and performing carbonization treatment in a nitrogen atmosphere, wherein the carbonization treatment temperature is 1200 ℃, and the time is 2h, thus obtaining the tin bismuth-carbon composite material.
Comparative example 1
The only difference from example 1 is that: the procedure of example 1 was repeated except that no tin salt was added.
Comparative example 2
The only difference from example 1 is that: acetylene black was not added, and the procedure of example 1 was repeated.
Comparative example 3
1g of a nitrogen-containing carbon source (polyacrylonitrile) and 10mL of dimethyl sulfoxide were mixed under stirring in an oil bath at 90℃to gel, and after cooling to room temperature, 1.5g of Bi (NO) was added to the resulting sol 3 ) 3 ·5H 2 O and 1.5g SnCl 4 ·5H 2 O, stirring and mixing uniformly to obtain a gel precursor;
calcining the gel precursor for 1h at 800 ℃ in a nitrogen atmosphere, and naturally cooling to obtain the tin-bismuth-carbon composite material.
Characterization of
SEM, EDS and TEM tests are carried out on the tin bismuth-carbon composite material prepared in the example 1, and the obtained results are shown in figures 1-3;
as can be seen from FIG. 1, the tin bismuth-carbon composite material prepared in example 1 has a spherical shape with a diameter of about 5. Mu.m.
As can be seen from the EDS element analysis of FIG. 2, the tin-bismuth-carbon composite material prepared in example 1 contains elements such as tin, bismuth and carbon, and the tin-bismuth-carbon composite material is proved to contain metallic tin and bismuth.
The TEM image of fig. 3 shows (200) lattice fringes of metallic tin and (012) lattice fringes of metallic bismuth, further confirming the successful preparation of metallic tin and metallic bismuth.
Test case
Tin bismuth-carbon composite Material prepared in example 1Mixing the material, a conductive agent (acetylene black) and a binder (polyvinylidene fluoride) according to the mass ratio of 8:1:1, and adding N-methyl pyrrolidone (NMP) to adjust the solid content of the mixed slurry to 30%; sealing the slurry, stirring at 500r/min for 24 hr, coating the uniformly stirred slurry on copper foil current collector, and controlling the density of coating layer to 2mg/cm 2 And (3) placing the prepared electrode plate into a vacuum drying oven at 90 ℃ for drying for 12 hours, taking out, and punching the electrode plate with the diameter of 12.5mm in a steel die.
The lithium metal sheet is used as a negative electrode, the electrode sheet is used as a positive electrode, a single-layer polypropylene material is used as a diaphragm, and a mixed solvent of dimethyl carbonate and ethyl cellulose (the volume ratio of the dimethyl carbonate to the ethyl cellulose is 1:1) is used for dissolving LiPF 6 Forming an electrolyte (LiPF) 6 Concentration of 1 mol/L), and placing the mixture in a glove box to assemble the CR2032 button half cell. After the assembled battery is placed for 24 hours, the electrochemical performance test is performed.
Adopting a Chenhua CHI660E electrochemical workstation to carry out cyclic voltammetry test, wherein the scanning speed is 0.1mV/s, and the scanning potential range is 0.01-3.0V; and adopting a CT2001B type blue electric battery test system, making an electrode material into a half battery, and testing constant current charge and discharge (rate capability and cycle capability) under different currents. At the time of the rate performance test, the current density was increased from 0.1A/g to 0.2A/g, 0.5A/g, 1.0A/g, 2.0A/g and 5.0A/g in order, and then returned to 0.2A/g. The current density used in the cycle performance test was 1.0A/g, and the results are shown in FIGS. 4 to 6.
The results show that:
from the cyclic voltammogram test of fig. 4, the second and third cycle curves substantially coincide after the first cycle, indicating that the material has good cycle reversibility.
As can be seen from fig. 5, the battery assembled from the tin-bismuth-carbon composite material prepared in example 1 has a first discharge capacity of 1241.7mAh/g, a first charge capacity of 968.5mAh/g, and a first coulomb efficiency of 78% at a current density of 0.05A/g, and exhibits a high charge-discharge capacity and a high first coulomb efficiency.
The tin bismuth-carbon composite material prepared in example 1 shows excellent rate performance at current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1.0A/g, 2.0A/g and 5.0A/g, and discharge capacities of 801.8mAh/g, 635.6mAh/g, 535mAh/g, 411.4mAh/g, 336mAh/g and 245.6mAh/g, respectively.
As can be seen from FIG. 6, the tin bismuth-carbon composite material prepared in example 1 was cycled 500 times at a current density of 1A/g, and the reversible capacity was still maintained at 289.1mAh/g.
The tin bismuth-carbon composite materials prepared in examples 2 to 3 have similar properties to those in example 1, and also have excellent rate performance and cycle performance.
The battery assembled by the tin bismuth-carbon composite material prepared in the comparative example 1 has a first discharge capacity of 1173.9mAh/g, a first charge capacity of 798.3mAh/g and a first coulomb efficiency of 68% at a current density of 0.05A/g; at current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1.0A/g, 2.0A/g and 5.0A/g, the discharge capacities were 603.5mAh/g, 536.1mAh/g, 436mAh/g, 312.3mAh/g, 231mAh/g and 146.5mAh/g, respectively; at a current density of 1A/g, the reversible capacity remained at 189.2mAh/g for 500 cycles.
The battery assembled by the tin bismuth-carbon composite material prepared in the comparative example 2 has a first discharge capacity of 1247.5mAh/g, a first charge capacity of 898.2mAh/g and a first coulomb efficiency of 72% at a current density of 0.05A/g; at current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1.0A/g, 2.0A/g and 5.0A/g, the discharge capacities were 756.8mAh/g, 585.3mAh/g, 495mAh/g, 392.3mAh/g, 295mAh/g and 205.3mAh/g, respectively; at a current density of 1A/g, the reversible capacity remained at 201.3mAh/g for 500 cycles.
The battery assembled by the tin bismuth-carbon composite material prepared in the comparative example 3 has a first discharge capacity of 1201.1mAh/g, a first charge capacity of 888.8mAh/g and a first coulomb efficiency of 74% at a current density of 0.05A/g; at current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1.0A/g, 2.0A/g and 5.0A/g, the discharge capacities were 736.5mAh/g, 601.3mAh/g, 501mAh/g, 381.4mAh/g, 306mAh/g and 216.1mAh/g, respectively; at a current density of 1A/g, the reversible capacity remained at 239.2mAh/g for 500 cycles.
In conclusion, the tin bismuth-carbon composite material prepared by the invention is used as a negative electrode material of a lithium ion battery, and excellent electrochemical performance can be obtained. In addition, the bismuth carbon composite nano-sheet provided by the invention can be used as a negative electrode material of a sodium/potassium ion secondary battery, and has good effect.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the tin bismuth-carbon composite material is characterized by comprising the following steps of:
mixing a nitrogen-containing carbon source and dimethyl sulfoxide under a heating condition, gelatinizing, and adding bismuth salt and tin salt into the obtained sol to obtain a gel precursor;
and mixing the gel precursor, the surfactant, the acetylene black and water, spray-drying the obtained liquid material, and carbonizing the liquid material in nitrogen or argon atmosphere to obtain the tin-bismuth-carbon composite material.
2. The method according to claim 1, wherein the nitrogen-containing carbon source comprises one or more of polyacrylonitrile, polyaniline, polyimide, melamine phenol resin, dicyandiamide phenol resin, and polyurethane; the heating temperature is 90-100 ℃.
3. The preparation method according to claim 1, wherein the bismuth salt comprises one or more of bismuth sulfate, bismuth nitrate pentahydrate, bismuth chloride and bismuth acetate; the tin salt comprises tin chloride pentahydrate; the mass ratio of the bismuth salt to the tin salt is 1:1-2.
4. The method according to claim 1 or 3, wherein the mass ratio of the bismuth salt to the nitrogen-containing carbon source is 1:1 to 3.
5. The preparation method according to claim 1, wherein the surfactant comprises one or more of cetyltrimethylammonium bromide, sodium dodecyl sulfate and polyvinylpyrrolidone; the mass ratio of the bismuth salt to the surfactant is 0.2-0.5:0.2-0.5.
6. The method according to claim 1, wherein the mass of the acetylene black is 5 to 10% of the total mass of the bismuth salt, the tin salt and the nitrogen-containing carbon source.
7. The method according to claim 1, wherein the spray drying temperature is 150 to 200 ℃, the spraying amount by the spraying system is 5 to 30mL/min, and the atomization pressure is 5 to 40MPa.
8. The method according to claim 1, wherein the carbonization treatment is carried out at a temperature of 800 to 1200 ℃ for a time of 2 to 5 hours.
9. The tin bismuth-carbon composite material prepared by the preparation method of any one of claims 1 to 8.
10. The use of the tin-bismuth-carbon composite material as claimed in claim 9 in lithium ion batteries, sodium ion batteries or potassium ion batteries.
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