CN109437123A - The ferrous disulfide carbon coating composite material and preparation method and application that selenium mixes - Google Patents
The ferrous disulfide carbon coating composite material and preparation method and application that selenium mixes Download PDFInfo
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- CN109437123A CN109437123A CN201811203277.9A CN201811203277A CN109437123A CN 109437123 A CN109437123 A CN 109437123A CN 201811203277 A CN201811203277 A CN 201811203277A CN 109437123 A CN109437123 A CN 109437123A
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- Prior art keywords
- selenium
- composite material
- mixes
- ferrous disulfide
- carbon coating
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- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 67
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 60
- 239000011669 selenium Substances 0.000 title claims abstract description 60
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 59
- 229940095991 ferrous disulfide Drugs 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 239000011248 coating agent Substances 0.000 title claims abstract description 41
- 238000000576 coating method Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 13
- 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 12
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000005864 Sulphur Substances 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 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
- 238000003763 carbonization Methods 0.000 claims description 6
- 239000002738 chelating agent Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- 229960001484 edetic acid Drugs 0.000 claims description 6
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 239000002904 solvent 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 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
- 235000006408 oxalic acid Nutrition 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 1
- 229930006000 Sucrose Natural products 0.000 claims 1
- 239000005720 sucrose Substances 0.000 claims 1
- 238000003860 storage Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 241000773945 Trimusculidae Species 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 230000003796 beauty Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- WALCGGIJOOWJIN-UHFFFAOYSA-N iron(ii) selenide Chemical class [Se]=[Fe] WALCGGIJOOWJIN-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229960003351 prussian blue Drugs 0.000 description 2
- 239000013225 prussian blue Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229910020657 Na3V2(PO4)3 Inorganic materials 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid 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
- 238000005255 carburizing Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- -1 diaphragm Substances 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002243 precursor 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
- VIDTVPHHDGRGAF-UHFFFAOYSA-N selenium sulfide Chemical compound [Se]=S VIDTVPHHDGRGAF-UHFFFAOYSA-N 0.000 description 1
- 229960005265 selenium sulfide Drugs 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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 present invention proposes a kind of ferrous disulfide carbon coating composite material that selenium mixes, and the group of the composite material becomes FeSexS2‑x@C, wherein the range of x is 0.1-1.9.The ferrous disulfide carbon coating composite material that selenium proposed by the present invention mixes, Volumetric expansion can effectively be inhibited by being applied in sodium-ion battery, improve actual specific capacity, high rate performance and cycle performance.The present invention also proposes the preparation method and application for the ferrous disulfide carbon coating composite material that the selenium mixes.
Description
Technical field
The present invention relates to a kind of ferrous disulfide carbon coating composite materials that selenium mixes, and further relate to preparation method and answer
With.
Background technique
Sodium element rich reserves, cheap (Na2CO3: 150 beauty yuan/ton), moreover, sodium be except lithium outer density it is minimum, from
The sub- the smallest alkali metal element of radius makes sodium-ion battery become most promising novel battery.In nearest research report,
The performance of sodium-ion battery positive material can match in excellence or beauty with the positive electrode of lithium ion battery, recklessly including Chinese Academy of Sciences's CAS Institute of Physics
The Na that Yong Sheng seminar, Chen Liquan seminar developxMO2Class anode [1-2], Guo Yuguo seminar, university, the Chinese Academy of Sciences, Shanghai
The prussian blue that Liao little Zhen seminar, university of communications develops is positive [3-4], Huang Yunhui seminar, the Central China University of Science and Technology, Hu Xianluo
The Na that seminar, Wang Xianyou seminar, University Of Xiangtan developxMy(PO4)z[5-6] such as Fw class anodes, charge/discharge capacity and circulation are steady
The qualitative requirement for all largely meeting business and using.
So the commercialized biggest obstacle of sodium-ion battery is that shortage specific capacity is high, voltage is suitable and stable
Negative electrode material.Metallic sodium itself punctures battery diaphragm due to being also easy to produce dendrite in charge and discharge process, is not appropriate for as cathode；
The graphite cathode interlamellar spacing of successful commercialization in lithium batteryLess than sodium ion diameterTo sodium ion
Without electro-chemical activity, but also studies have reported that make graphite expansion using electrolyte diethylene glycol dimethyl ether or oxidation means, stored up
Sodium [7-8]；In addition, Hu Yongsheng seminar has developed the TiO having good stability2/NaMxTiyOzNa-like ions battery cathode [9]；
However, the reversible specific capacity of the lamellar compound of these intercalations storage sodium is universal relatively low (25~350mAh/g).
Pyrite (ferrous disulfide) a very long time, by as lithium ion battery material, it is low to be primarily due to its price
Honest and clean, rich reserves are environmental-friendly and cheap.Primary battery using it as raw material has more preferable compared with alkaline battery of equal value
High rate performance and more excellent working life.And two selenium ferrous irons are rarely found in the report of energy storage field.It is nearest in lu [10]
Work in, Nanoscale Iron selenides (FeSe is prepared for using sonication2), it is found that it shows to show in sodium ion storage
The activity of work.The laboratory carries out in pyrosol, keeps it evenly dispersed in non-polar organic solvent.It is prepared
FeSe2Nano particle shows very high specific capacity, high rate performance and good cyclical stability.The iron of sonication preparation
Selenides still inevitably generates Volumetric expansion after long-time recycles.
The drawbacks of to overcome early-stage study, we devise the preparation method of solvent heat, are prepared for selenium sulfide, and use
The cladding carbonization of polymer low temperature, overcomes the problems, such as its volume expansion.
[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 Na2Ti3O7for 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.；
WuT.P.；Li Y.G.；Lu J..Improved Sodium-Ion Storage Performance of Ultrasmall
Iron Selenide Nanoparticles.Nano Lett.2017,17,4137-4142.
Summary of the invention
To solve problem of the prior art, the present invention proposes a kind of ferrous disulfide carbon coating composite material that selenium mixes,
Volumetric expansion can effectively be inhibited by being applied in sodium-ion battery, improve actual specific capacity, high rate performance and cycle performance.
The present invention also proposes a kind of preparation method and application of ferrous disulfide carbon coating composite material that the selenium mixes.
The present invention proposes a kind of ferrous disulfide carbon coating composite material that selenium mixes, and the group of the composite material becomes
FeSexS2-x@C, wherein the range of x is 0.1-1.9.That is the ferrous disulfide that mixes of carbon coating selenium, wherein ferrous disulfide and selenium
Substance amount ratio be X:2 subtract X.
The present invention also proposes the preparation method for the ferrous disulfide carbon coating composite material that selenium described in one kind mixes, including
Following steps:
S1, the preparation for the ferrous disulfide that selenium mixes
S1.1 prepares the solution FeL containing ferrous iony, wherein L is acid ion, ferrous ion concentration 0.2-
2mol/L；Sulphur powder, selenium powder and carbon dust is added, the solution is adjusted to strong basicity；
S1.2 is added after reducing agent and chelating agent after mixing, puts into crystal seed；
S1.3 reacts 20-30h under 130-145 DEG C of reaction condition and obtains the ferrous disulfide that selenium mixes；
S2, the preparation for the ferrous disulfide carbon coating composite material that selenium mixes
S.2.1, use phosphorus content for 90% or more Identification of Soluble Organic polyphenyl acetylenic polymer as carbon source, by the carbon source
Be dissolved in pair/Resorcino solvent in, be configured to the polymer solution that mass fraction is 0.5%~4%；
S.2.2, ferrous disulfide grinding refinement selenium made from step S1.3 mixed, disperses under the auxiliary of ultrasonic wave
To in the polymer solution；
S.2.3, after being evaporated solution in nitrogen protection atmosphere, using ethanol washing and in 90 DEG C of vacuum drying 10h；
S.2.4, the product after vacuum drying is ground, be placed at 300 DEG C of tube furnace, keep 30min be allowed to
Sufficiently carbonization obtains the ferrous disulfide carbon coating composite material that selenium mixes.
Further, the acid ion is Cl-、SO4 2-、NO3 -Or CH3COO-One or more of.
Further, carbon dust by mass fraction is that 0.1%-10% is added in step S1.1, and the total amount of sulphur powder and selenium powder
According to stoichiometric ratio excess 5%-30%.
Further, the reducing agent is citric acid, malic acid, oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butanal, sugarcane
One of sugar, ethanedioic acid, adipic acid or two kinds or more, reducing agent additive amount are stoichiometrically number excessive 10%.
Further, the chelating agent is ethylenediamine tetra-acetic acid, and additive amount is 3~30wt%.
Further, the crystal seed is NiSe2Or FeSe2One or both of.The available high-purity of the addition of crystal seed
The selenium of controllable Se content adulterates ferrous disulfide.
Present invention further propose that the application for the ferrous disulfide carbon coating composite material that the selenium mixes: will be described
The ferrous disulfide carbon coating composite material that selenium mixes is applied in sodium-ion battery as negative electrode material.
Further, the positive electrode of the sodium-ion battery is metallic sodium, and electrolyte is 1M NaPF6。
Beneficial effects of the present invention:
Ferrous disulfide shows significant activity in sodium ion storage in composite material of the invention, and especially selenium is mixed
Miscellaneous ferrous disulfide, can effectively improve electro-chemical activity, have high specific capacity and high rate performance.Composite wood of the invention
Expect that the ferrous disulfide particle surface adulterated in selenium coats one layer of carbon film, can effectively inhibit Volumetric expansion, improves practical
Specific capacity, high rate performance and cycle performance.
Preparation method of the invention uses solution combined method, fast and effeciently can adulterate ferrous disulfide in selenium
Grain surface forms one layer of carbon film, and the carbon content of finished product is 2%~10%, in addition, this method is made using high-carbon content polymer
For carbon matrix precursor, carbon content is high, and carburizing temperature is low, and carbonization time is short.
Detailed description of the invention
Fig. 1 is FeSe prepared by the embodiment of the present invention 10.2S1.8@C composite exists as the sodium-ion battery of cathode
Cycle performance under 500mA.
Fig. 2 is FeSe prepared by the embodiment of the present invention 10.2S1.8Multiplying power of the@C composite as the sodium-ion battery of cathode
Performance.
Fig. 3 is FeSe prepared by the embodiment of the present invention 21S1@C composite as cathode sodium-ion battery at 500mA
Cycle performance.
Fig. 4 is FeSe prepared by the embodiment of the present invention 21S1@C composite as cathode sodium-ion battery it is forthright again
Energy.
Specific embodiment
As follows in conjunction with attached drawing, application scheme is further described:
Embodiment 1
The group of a kind of ferrous disulfide carbon coating composite material that selenium mixes, the composite material becomes FeSexS2-x@C,
Wherein x is 0.2, i.e. the group of composite material becomes FeSe0.2S1.8@C。
A kind of preparation method for the ferrous disulfide carbon coating composite material that above-mentioned selenium mixes, comprising the following steps:
S1, the preparation for the ferrous disulfide that selenium mixes
S1.1 prepares the solution FeSO containing ferrous ion in a kettle4, ferrous ion concentration 1.0mol/L；Add
Enter sulphur powder, selenium powder and carbon dust, wherein carbon powder content is the 5% of solution, and the molar ratio for controlling selenium powder and sulphur powder is 1:9, this is molten
Liquid is adjusted to strong basicity.
S1.2, the stoichiometrically citric acids of number excessive 10% and ascorbic acid is added, and (molar ratio of two kinds of reducing agents is
1:1) 1% NiSe is put into after mixing as chelating agent as the ethylenediamine tetra-acetic acid (EDTA) of reducing agent and 8wt%2
With 1% FeSe2As crystal seed.
Reaction kettle is put into baking oven by S1.3, is reacted under 130-140 DEG C of reaction condition and is obtained selenium mixes two for 24 hours
Ferrous sulfide.
S2, the preparation for the ferrous disulfide carbon coating composite material that selenium mixes
S.2.1, use phosphorus content for 90% or more Identification of Soluble Organic polyphenyl acetylenic polymer as carbon source, by the carbon source
Be dissolved in pair/Resorcino solvent in, be configured to the polymer solution that mass concentration is 4%.
S.2.2, ferrous disulfide grinding refinement selenium made from step S1.3 mixed, disperses under the auxiliary of ultrasonic wave
To in the polymer solution.
S.2.3, after being evaporated solution in nitrogen protection atmosphere, using ethanol washing and in 90 DEG C of vacuum drying 10h.
S.2.4, the product after vacuum drying is ground, be placed at 300 DEG C of tube furnace, keep 30min be allowed to
Sufficiently carbonization obtains the ferrous disulfide carbon coating composite material FeSe that selenium mixes0.2S1.8@C。
A kind of application for the ferrous disulfide carbon coating composite material that above-mentioned selenium mixes:
The ferrous disulfide carbon coating composite material FeSe that the selenium is mixed0.2S1.8@C is applied to as negative electrode material
In sodium-ion battery.Specifically, the positive electrode of the sodium-ion battery is metallic sodium, electrolyte is 1M NaPF6, using aluminium
Foil is as collector, by CR2016 button shell according to cathode housing, collector, anode electrode, electrolyte, diaphragm, electrolysis
Liquid, negative electrode, anode housing sequence successively stack compression and be assembled into sodium-ion battery, characterize its chemical property, follow
Ring stability and high rate performance are as depicted in figs. 1 and 2, the ferrous disulfide carbon coating composite wood that selenium manufactured in the present embodiment mixes
Material, cyclical stability is good, electrochemical performance.
Embodiment 2
The group of a kind of ferrous disulfide carbon coating composite material that selenium mixes, the composite material becomes FeSexS2-x@C,
Wherein x is 1, i.e. the group of composite material becomes FeSe1S1@C。
A kind of preparation method for the ferrous disulfide carbon coating composite material that above-mentioned selenium mixes, comprising the following steps:
S1, the preparation for the ferrous disulfide that selenium mixes
S1.1 prepares the solution FeSO containing ferrous ion in a kettle4, ferrous ion concentration 1mol/L；It is added
Sulphur powder, selenium powder and carbon dust, wherein carbon powder content is the 5% of solution, and the molar ratio for controlling selenium powder and sulphur powder is 1:1, by the solution
It is adjusted to strong basicity.
S1.2, be added the stoichiometrically citric acids of number excessive 10% and ascorbic acid (two kinds of reducing agent molar ratios are 1:
1) 1% NiSe is put into after mixing as chelating agent as reducing agent and 8wt% ethylenediamine tetra-acetic acid (EDTA)2With
1% FeSe2As crystal seed.
Reaction kettle is put into baking oven by S1.3, is reacted under 130-140 DEG C of reaction condition and is obtained selenium mixes two for 24 hours
Ferrous sulfide.
S2, the preparation for the ferrous disulfide carbon coating composite material that selenium mixes
S.2.1, use phosphorus content for 90% or more Identification of Soluble Organic polyphenyl acetylenic polymer as carbon source, by the carbon source
Be dissolved in pair/Resorcino solvent in, be configured to the polymer solution that mass concentration is 4%.
S.2.2, ferrous disulfide grinding refinement selenium made from step S1.3 mixed, disperses under the auxiliary of ultrasonic wave
To in the polymer solution.
S.2.3, after being evaporated solution in nitrogen protection atmosphere, using ethanol washing and in 90 DEG C of vacuum drying 10h.
S.2.4, the product after vacuum drying is ground, be placed at 300 DEG C of tube furnace, keep 30min be allowed to
Sufficiently carbonization obtains the ferrous disulfide carbon coating composite material FeSe that selenium mixes1S1@C。
A kind of application for the ferrous disulfide carbon coating composite material that above-mentioned selenium mixes:
The ferrous disulfide carbon coating composite material FeSe that the selenium is mixed1S1@C is applied to sodium as negative electrode material
In ion battery.Specifically, the positive electrode of the sodium-ion battery is metallic sodium, electrolyte is 1M NaPF6, using aluminium foil
As collector, by CR2016 button shell according to cathode housing, collector, anode electrode, electrolyte, diaphragm, electrolyte,
Negative electrode, anode housing sequence successively stack compression and be assembled into sodium-ion battery, characterize its chemical property, circulation is steady
Qualitative and high rate performance is as shown in Figure 3 and Figure 4, the ferrous disulfide carbon coating composite material that selenium manufactured in the present embodiment mixes,
Cyclical stability is good, electrochemical performance.
It is that above-mentioned preferred embodiment should be regarded as application scheme embodiment for example, all with application scheme thunder
Same, approximate or technology deduction, replacement, improvement for making based on this etc., are regarded as the protection scope of this patent.
Claims (9)
1. a kind of ferrous disulfide carbon coating composite material that selenium mixes, which is characterized in that the group of the composite material becomes
FeSexS2-x@C, wherein the range of x is 0.1-1.9.
2. a kind of preparation method for the ferrous disulfide carbon coating composite material that selenium described in claim 1 mixes, feature exist
In, comprising the following steps:
S1, the preparation for the ferrous disulfide that selenium mixes
S1.1 prepares the solution FeL containing ferrous iony, wherein L is acid ion, ferrous ion concentration 0.2-2mol/L；
Sulphur powder, selenium powder and carbon dust is added, the solution is adjusted to strong basicity；
S1.2 is added after reducing agent and chelating agent after mixing, puts into crystal seed；
S1.3 reacts 20-30h under 130-145 DEG C of reaction condition and obtains the ferrous disulfide that selenium mixes；
S2, the preparation for the ferrous disulfide carbon coating composite material that selenium mixes
S.2.1, use phosphorus content for 90% or more Identification of Soluble Organic polyphenyl acetylenic polymer as carbon source, which is dissolved
In right/Resorcino solvent, it is configured to the polymer solution that mass fraction is 0.5%~4%；
S.2.2, ferrous disulfide grinding refinement selenium made from step S1.3 mixed, is dispersed to institute under the auxiliary of ultrasonic wave
It states in polymer solution；
S.2.3, after being evaporated solution in nitrogen protection atmosphere, using ethanol washing and in 90 DEG C of vacuum drying 10h；
S.2.4, the product after vacuum drying is ground, be placed at 300 DEG C of tube furnace, keep 30min be allowed to abundant
Carbonization obtains the ferrous disulfide carbon coating composite material that selenium mixes.
3. the preparation method for the ferrous disulfide carbon coating composite material that selenium according to claim 2 mixes, feature exist
In the acid ion is Cl-、SO4 2-、NO3 -Or CH3COO-One or more of.
4. the preparation method for the ferrous disulfide carbon coating composite material that selenium according to claim 2 mixes, feature exist
In carbon dust is 0.1%-10% addition by mass fraction in step S1.1, and sulphur powder and the total amount of selenium powder are according to stoichiometric ratio
Excessive 5%-30%.
5. the preparation method for the ferrous disulfide carbon coating composite material that selenium according to claim 2 mixes, feature exist
In, the reducing agent be citric acid, malic acid, oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butanal, sucrose, ethanedioic acid, oneself two
One of acid or two kinds or more, reducing agent additive amount are stoichiometrically number excessive 10%.
6. the preparation method for the ferrous disulfide carbon coating composite material that selenium according to claim 2 mixes, feature exist
In the chelating agent is ethylenediamine tetra-acetic acid, and additive amount is 3~30wt%.
7. the preparation method for the ferrous disulfide carbon coating composite material that selenium according to claim 2 mixes, feature exist
In the crystal seed is NiSe2Or FeSe2One or both of.
8. a kind of application for the ferrous disulfide carbon coating composite material that selenium described in claim 1 mixes, which is characterized in that will
The ferrous disulfide carbon coating composite material that the selenium mixes is applied in sodium-ion battery as negative electrode material.
9. the application for the ferrous disulfide carbon coating composite material that selenium according to claim 8 mixes, which is characterized in that institute
The positive electrode for stating sodium-ion battery is metallic sodium, and electrolyte is 1M NaPF6。
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