CN109437123B - Selenium-doped ferrous disulfide carbon-coated composite material and preparation method and application thereof - Google Patents
Selenium-doped ferrous disulfide carbon-coated composite material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229940095991 ferrous disulfide Drugs 0.000 title claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 28
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 11
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002738 chelating agent Substances 0.000 claims description 6
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910019398 NaPF6 Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 150000005837 radical ions Chemical class 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 229960001484 edetic acid Drugs 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- WALCGGIJOOWJIN-UHFFFAOYSA-N iron(ii) selenide Chemical compound [Se]=[Fe] WALCGGIJOOWJIN-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- VIDTVPHHDGRGAF-UHFFFAOYSA-N selenium sulfide Chemical compound [Se]=S VIDTVPHHDGRGAF-UHFFFAOYSA-N 0.000 description 2
- 229960005265 selenium sulfide Drugs 0.000 description 2
- 244000175448 Citrus madurensis Species 0.000 description 1
- 235000017317 Fortunella Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
-
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- 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 provides a selenium-doped ferrous disulfide carbon-coated composite material, which comprises FeSexS2‑x@ C, where x ranges from 0.1 to 1.9. The selenium-doped ferrous disulfide carbon-coated composite material provided by the invention can be applied to a sodium ion battery to effectively inhibit the volume expansion effect and improve the actual specific capacity, rate capability and cycle performance. The invention also provides a preparation method and application of the selenium-doped ferrous disulfide carbon-coated composite material.
Description
Technical Field
The invention relates to a selenium-doped ferrous disulfide carbon-coated composite material, and also relates to a preparation method and application thereof.
Background
The sodium element has rich storage and low price (Na)2CO3: $ 150/ton), and sodium is the lowest density alkali metal element, with the smallest ionic radius, except for lithium, making sodium-ion batteries the most promising new battery. In recent research reports, the performance of positive electrode materials of sodium ion batteries is comparable to that of positive electrode materials of lithium ion batteries, including Na developed by the heroic win subject group and the standing spring subject group in the physical institute of Chinese academy of sciencesxMO2Quasi-positive pole [1-2]Group of subjects of Guo Yu national university of Chinese academy of sciencesPrussian blue positive electrode [3-4 ] developed by Liao Xiaozhen subject group of sea transportation university]Na developed by Huangyunhui subject group, kumquat subject group, Hunan lake university and Kingmr subject group of Huazhong science and technology universityxMy(PO4)zFw type positive electrode and the like [5-6]The charge-discharge capacity and the cycle stability both meet the requirements of commercial use to a great extent.
Therefore, the greatest obstacle to commercialization of sodium ion batteries is the lack of a negative electrode material with high specific capacity, suitable voltage, and stability. The metal sodium is not suitable for being used as a negative electrode because dendrite is easily generated to pierce a battery diaphragm in the charging and discharging processes; the negative electrode interlayer spacing (1.86 a) of graphite successfully commercialized in lithium batteries is smaller than the sodium ion diameter (2.04 a), and is electrochemically inactive to sodium ions, but studies have also reported that graphite is expanded using electrolyte diglyme or an oxidizing means to store sodium [7-8 ]](ii) a In addition, a group of issues of wonderful success developed TiO with good stability2/NaMxTiyOzSimilar sodium ion battery cathode [9 ]]However, the reversible specific capacity of these intercalated sodium-storing layered compounds is generally low (25-350 mAh/g).
Pyrite (ferrous disulfide) has been used as a lithium ion battery material for a long time, mainly because of its low price, abundant reserves, environmental friendliness and low price. The primary battery using the alkaline electrolyte as a raw material has better rate capability and more excellent service life than an equivalent alkaline battery. While few reports of ferrous diselenide in the field of energy storage are available. In lu [10 ]]In recent work, nano iron selenide (FeSe) is prepared by ultrasonic means2) It was found to exhibit significant activity in sodium ion storage. The laboratory was run in high temperature solution, which was uniformly dispersed in a non-polar organic solvent. Prepared FeSe2The nanoparticles exhibit high specific capacity, rate capability and good cycling stability. The iron selenide prepared by the ultrasonic means still can not avoid the volume expansion effect after long-time circulation.
In order to overcome the defects of earlier research, a solvothermal preparation method is designed, selenium sulfide is prepared, and a polymer is coated and carbonized at low temperature, so that the problem of volume expansion of the selenium sulfide is solved.
[1].Pan, H. L., Hu, Y. S., Chen, L. Q., Room-Temperature Stationary Sodium-Ion Batteries for Large-Scale Electric Energy Storage. Energy Environ. Sci., 2013, 6(8), 2338-2360.
[2]. Mu, L. Q.; Xu, S. Y.; Li, Y. M.; Hu, Y. S.; Li H.; Chen L. Q.; Huang X. J., Prototype Sodium-Ion Batteries Using an Air-Stable and Co/Ni-Free O3-Layered Metal Oxide Cathode. Adv. Mater., 2015, 27(43), 6928-6933.
[3]. You, Y.; Wu, X. L.; Yin, Y. X.; Guo, Y. G., High-quality Prussian Blue Crystals as Superior Cathode Materials for Room-Temperature Sodium-Ion Batteries. Energy Environ Sci, 2014, 7(5),1643-1647.
[4]. Yang, D. Z.; Xu, J.; Liao, X. Z.; He, Y. S.; Liu, H. M.; Ma, Z. F., Structure Optimization of Prussian Blue Analogue Cathode Materials for Advanced Sodium Ion Batteries. Chem. Commun.2014, 50(87), 13377-13380.
[5]. Zhang, W.; Liu, Y. T.; Chen, C. J.; Li, Z.; Huang, Y. H.; Hu, X. L., Flexible and Binder-Free Electrodes of Sb/rGO and Na3V2(PO4)3/rGO Nanocomposites for Sodium-Ion Batteries. Small2015, 11 (31), 3822-3829.
[6]. Zhuo, H. T.; Wang, X. Y.; Tang, A. P.; Liu, Z. M.; Gamboa, S.; Sebastian, P. J., The preparation of NaV1− x CrxPO4F cathode materials for sodium-ion battery. J. Power Sources 2006, 160 (1), 698-703.
[7]. Jache, B.; Adelhelm, P., Use of Graphite as a Highly Reversible Electrode with Superior Cycle Life for Sodium-Ion Batteries by Making Use of Co-Intercalation Phenomena. Angew. Chem.-Int.Edit. 2014, 53 (38), 10169-10173.
[8]. Wen, Y.; He, K.; Zhu, Y. J.; Han, F. D.; Xu, Y. H.; Matsuda, I.; Ishii, Y.; Cumings, J.; Wang, C. S., Expanded graphite as superior anode for sodium-ion batteries. Nat. Commun. 2014, 5,4033-4042.
[9]. Pan, H. L.; Lu, X.; Yu, X. Q.; Hu, Y. S.; Li, H.; Yang, X. Q.; Chen, L. Q., Sodium Storage and Transport Properties in Layered Na2Ti3O7 for Room-Temperature Sodium-Ion Batteries. Adv.Energy Mater. 2013, 3 (9), 1186-1194.
[10]. Zhao F.P.; Shen S.D.; Cheng L.; Ma L.; Zhou J.H.; Ye H. L.; Han N.; Wu T. P.; Li Y. G.; Lu J..Improved Sodium-Ion Storage Performance of Ultrasmall Iron Selenide Nanoparticles. Nano Lett. 2017, 17, 4137−4142.。
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a selenium-doped ferrous disulfide carbon-coated composite material which can effectively inhibit the volume expansion effect and improve the actual specific capacity, rate capability and cycle performance when applied to a sodium ion battery. The invention also provides a preparation method and application of the selenium-doped ferrous disulfide carbon-coated composite material.
The invention provides a preparation method of a selenium-doped ferrous disulfide carbon-coated composite material, which is characterized in that the composite material consists of FeSexS2-x @ C, wherein the range of x is 0.1-1.9, and the preparation method comprises the following steps:
s1 preparation of selenium-doped ferrous disulfide
S1.1, preparing a solution FeL containing ferrous ionsyWherein L is acid radical ion, and the concentration of ferrous ion is 0.2-2 mol/L; adding sulfur powder, selenium powder and carbon powder, and adjusting the solution to be strong alkaline;
s1.2, adding a reducing agent and a chelating agent, uniformly mixing, and then adding seed crystals; the chelating agent is ethylenediamine tetraacetic acid, the addition amount is 3-30 wt%, the seed crystal is one or two of NiSe2 or FeSe2, and the seed crystal is added to obtain the selenium-doped ferrous disulfide with high purity and controllable selenium content;
s1.3, reacting for 20-30h under the reaction condition of 130-145 ℃ to obtain selenium-doped ferrous disulfide;
s2 preparation of selenium-doped ferrous disulfide carbon-coated composite material
S.2.1, adopting an organic soluble polyphenylacetylene polymer with carbon content of more than 90% as a carbon source, dissolving the carbon source in a p/m-diphenol solvent, and preparing into a polymer solution with the mass fraction of 0.5% -4%;
s.2.2, grinding and refining the selenium-doped ferrous disulfide prepared in the step S1.3, and dispersing the selenium-doped ferrous disulfide into the polymer solution under the assistance of ultrasonic waves;
s.2.3, evaporating the solution to dryness in a nitrogen protective atmosphere, washing with ethanol, and vacuum-drying at 90 ℃ for 10 hours;
and S.2.4, grinding the product after vacuum drying, and then placing the product in a tubular furnace at 300 ℃ for 30min to fully carbonize the product to obtain the selenium-doped ferrous disulfide carbon-coated composite material.
Further, the acid radical ion is Cl-、SO4 2-、NO3 -Or CH3COO-One or more than two of them.
Further, in the step S1.1, 0.1-10% of carbon powder is added by mass, and the total amount of sulfur powder and selenium powder is 5-30% of the stoichiometric excess.
Furthermore, the reducing agent is one or more than two of citric acid, malic acid, oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butyl aldehyde, sucrose, oxalic acid and adipic acid, and the addition amount of the reducing agent is 10% excess according to stoichiometric amount.
Further, the selenium-doped ferrous disulfide carbon-coated composite material is prepared by the preparation method, namely the carbon-coated selenium-doped ferrous disulfide, wherein the mass ratio of the ferrous disulfide to the selenium is X: 2 minus X.
Further, a selenium-doped ferrous disulfide carbon-coated composite material prepared by the preparation method of claim 1.
The invention further provides an application of the selenium-doped ferrous disulfide carbon-coated composite material, which comprises the following steps: the selenium-doped ferrous disulfide carbon-coated composite material is applied to a sodium ion battery as a negative electrode material.
Furthermore, the positive electrode material of the sodium ion battery is metal sodium, and the electrolyte is 1M NaPF6。
The invention has the beneficial effects that:
the ferrous disulfide in the composite material shows remarkable activity in sodium ion storage, and particularly the selenium-doped ferrous disulfide can effectively improve the electrochemical activity and has high specific capacity and rate capability. The composite material disclosed by the invention has the advantages that the carbon film is coated on the surface of the selenium-doped ferrous disulfide particles, so that the volume expansion effect can be effectively inhibited, and the actual specific capacity, rate capability and cycle performance are improved.
The preparation method adopts a solution compounding method, can quickly and effectively form a layer of carbon film on the surfaces of selenium-doped ferrous disulfide particles, and the carbon content of a finished product is 2-10%.
Drawings
FIG. 1 shows FeSe prepared in example 1 of the present invention0.2S1.8The circulation performance of the sodium ion battery with the @ C composite material as the negative electrode is 500 mA.
FIG. 2 shows FeSe prepared in example 1 of the present invention0.2S1.8Rate capability of sodium ion battery with @ C composite material as negative electrode.
FIG. 3 shows FeSe prepared in example 2 of the present invention1S1The cycling performance of the sodium ion battery with the @ C composite material as the negative electrode at 500 mA.
FIG. 4 shows FeSe prepared in example 2 of the present invention1S1Rate capability of sodium ion battery with @ C composite material as negative electrode.
Detailed Description
The application scheme is further described below with reference to the accompanying drawings:
example 1
A selenium-doped ferrous disulfide carbon-coated composite material comprises FeSexS2-x@ C, where x is 0.2, i.e. the composition of the composite material is FeSe0.2S1.8@C。
A preparation method of the selenium-doped ferrous disulfide carbon-coated composite material comprises the following steps:
s1 preparation of selenium-doped ferrous disulfide
S1.1, preparing a solution FeSO containing ferrous ions in a reaction kettle4The ferrous ion concentration is 1.0 mol/L; adding sulfur powder, selenium powder and carbon powder, wherein the content of the carbon powder is 5 percent of that of the solution, controlling the molar ratio of the selenium powder to the sulfur powder to be 1:9, and adjusting the solution to be strong alkaline.
S1.2, adding citric acid and ascorbic acid (the molar ratio of the two reducing agents is 1: 1) which are excessive by 10 percent according to stoichiometric number as reducing agents and Ethylene Diamine Tetraacetic Acid (EDTA) which is 8 weight percent as chelating agents, uniformly mixing, and adding 1 percent of NiSe2And 1% of FeSe2As a seed crystal.
S1.3, placing the reaction kettle into an oven, and reacting for 24 hours under the reaction condition of 130-140 ℃ to obtain selenium-doped ferrous disulfide.
S2 preparation of selenium-doped ferrous disulfide carbon-coated composite material
S.2.1, adopting an organic soluble polyphenylacetylene polymer with the carbon content of more than 90 percent as a carbon source, and dissolving the carbon source in a p/m-diphenol solvent to prepare a polymer solution with the mass concentration of 4 percent.
S.2.2, grinding and refining the selenium-doped ferrous disulfide prepared in the step S1.3, and dispersing the selenium-doped ferrous disulfide into the polymer solution under the assistance of ultrasonic waves.
S.2.3, after the solution is evaporated to dryness in a nitrogen protective atmosphere, washing with ethanol and vacuum drying at 90 ℃ for 10 h.
S.2.4, grinding the product after vacuum drying, then placing the product in a tubular furnace at 300 ℃, keeping the temperature for 30min to fully carbonize the product to obtain the selenium-doped ferrous disulfide carbon-coated composite material FeSe0.2S1.8@C。
The application of the selenium-doped ferrous disulfide carbon-coated composite material comprises the following steps:
the selenium-doped ferrous disulfide carbon-coated composite material FeSe0.2S1.8@ C is applied to a sodium ion battery as a negative electrode material. Specifically, the positive electrode material of the sodium ion battery is metal sodium, and the electrolyte is 1The M NaPF6 adopts aluminum foil as a current collector, and a sodium ion battery is assembled by sequentially stacking and compressing a CR2016 button type shell according to the sequence of a positive shell, the current collector, a positive electrode, electrolyte, a diaphragm, the electrolyte, a negative electrode and a negative shell, so that the electrochemical performance of the sodium ion battery is represented, and the cycling stability and the rate capability of the sodium ion battery are shown in figures 1 and 2.
Example 2
A selenium-doped ferrous disulfide carbon-coated composite material comprises FeSexS2-x@ C, where x is 1, i.e. the composition of the composite material is FeSe1S1@C。
A preparation method of the selenium-doped ferrous disulfide carbon-coated composite material comprises the following steps:
s1 preparation of selenium-doped ferrous disulfide
S1.1, preparing a solution FeSO containing ferrous ions in a reaction kettle4The ferrous ion concentration is 1 mol/L; adding sulfur powder, selenium powder and carbon powder, wherein the content of the carbon powder is 5 percent of that of the solution, controlling the molar ratio of the selenium powder to the sulfur powder to be 1:1, and regulating the solution to be strong alkaline.
S1.2, adding citric acid and ascorbic acid (the molar ratio of the two reducing agents is 1: 1) which are excessive by 10 percent according to stoichiometric number as reducing agents and 8 weight percent of Ethylene Diamine Tetraacetic Acid (EDTA) as chelating agents, uniformly mixing, and adding 1 percent of NiSe2And 1% of FeSe2As a seed crystal.
S1.3, placing the reaction kettle into an oven, and reacting for 24 hours under the reaction condition of 130-140 ℃ to obtain selenium-doped ferrous disulfide.
S2 preparation of selenium-doped ferrous disulfide carbon-coated composite material
S.2.1, adopting an organic soluble polyphenylacetylene polymer with the carbon content of more than 90 percent as a carbon source, and dissolving the carbon source in a p/m-diphenol solvent to prepare a polymer solution with the mass concentration of 4 percent.
S.2.2, grinding and refining the selenium-doped ferrous disulfide prepared in the step S1.3, and dispersing the selenium-doped ferrous disulfide into the polymer solution under the assistance of ultrasonic waves.
S.2.3, evaporating the solution to dryness in a nitrogen protective atmosphere, washing with ethanol and drying in vacuum at 90 ℃ for 10 h.
S.2.4, grinding the product after vacuum drying, then placing the product in a tubular furnace at 300 ℃, keeping the temperature for 30min to fully carbonize the product to obtain the selenium-doped ferrous disulfide carbon-coated composite material FeSe1S1@C。
The application of the selenium-doped ferrous disulfide carbon-coated composite material comprises the following steps:
the selenium-doped ferrous disulfide carbon-coated composite material FeSe1S1@ C is applied to a sodium ion battery as a negative electrode material. Specifically, the positive electrode material of the sodium ion battery is metal sodium, the electrolyte is 1M NaPF6, an aluminum foil is used as a current collector, the sodium ion battery is assembled by sequentially stacking and compressing a CR2016 button-type shell according to the sequence of a positive electrode shell, a current collector, a positive electrode, an electrolyte, a diaphragm, the electrolyte, a negative electrode and a negative electrode shell, and the electrochemical performance of the sodium ion battery is represented, and the cycle stability and the rate capability of the sodium ion battery are shown in fig. 3 and 4.
The above preferred embodiments should be considered as examples of the embodiments of the present application, and technical deductions, substitutions, improvements and the like similar to, similar to or based on the embodiments of the present application should be considered as the protection scope of the present patent.
Claims (7)
1. A preparation method of a selenium-doped ferrous disulfide carbon-coated composite material is characterized in that the composite material is FeSexS2-x @ C, wherein x is in the range of 0.1-1.9, and the preparation method comprises the following steps:
s1 preparation of selenium-doped ferrous disulfide
S1.1, preparing solution FeL containing ferrous ionsyWherein L is acid radical ion, and the concentration of ferrous ion is 0.2-2 mol/L; adding sulfur powder, selenium powder and carbon powder, and adjusting the solution to strongAlkalinity;
s1.2, adding a reducing agent and a chelating agent, uniformly mixing, and then adding seed crystals, wherein the chelating agent is ethylenediamine tetraacetic acid, the addition amount is 3-30 wt%, and the seed crystals are one or two of NiSe2 or FeSe 2;
s1.3, reacting for 20-30h under the reaction condition of 130-145 ℃ to obtain selenium-doped ferrous disulfide;
s2 preparation of selenium-doped ferrous disulfide carbon-coated composite material
S.2.1, adopting an organic soluble polyphenylacetylene polymer with carbon content of more than 90% as a carbon source, dissolving the carbon source in a p/m-diphenol solvent, and preparing into a polymer solution with the mass fraction of 0.5% -4%;
s.2.2, grinding and refining the selenium-doped ferrous disulfide prepared in the step S1.3, and dispersing the selenium-doped ferrous disulfide into the polymer solution under the assistance of ultrasonic waves;
s.2.3, evaporating the solution to dryness in a nitrogen protective atmosphere, washing with ethanol, and vacuum-drying at 90 ℃ for 10 hours;
and S.2.4, grinding the product after vacuum drying, and then placing the product in a tubular furnace at 300 ℃ for 30min to fully carbonize the product to obtain the selenium-doped ferrous disulfide carbon-coated composite material.
2. The method of claim 1, wherein the acid ion is Cl-、SO4 2-、NO3 -Or CH3COO-One or more than two of them.
3. The method for preparing the selenium-doped ferrous disulfide carbon-coated composite material according to claim 1, wherein the carbon powder is added in the step S1.1 according to the mass fraction of 0.1-10%, and the total amount of the sulfur powder and the selenium powder is 5-30% excessive according to the stoichiometric ratio.
4. The method for preparing the selenium-doped ferrous disulfide carbon-coated composite material according to claim 1, wherein the reducing agent is one or more of citric acid, malic acid, oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butyraldehyde, sucrose, oxalic acid and adipic acid, and the addition amount of the reducing agent is 10% excess by stoichiometric amount.
5. A selenium-doped ferrous disulfide carbon-coated composite material characterized by being prepared by the preparation method of claim 1.
6. The use of the selenium-doped ferrous disulfide carbon coated composite of claim 1, wherein the selenium-doped ferrous disulfide carbon coated composite is used as a negative electrode material in a sodium ion battery.
7. The use of the selenium-doped ferrous disulfide carbon-coated composite material as claimed in claim 6, wherein the positive electrode material of the sodium ion battery is metallic sodium and the electrolyte is 1M NaPF6。
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