CN108172406A - One kind is with FeS2-xSexMaterial is the sodium ion capacitor of negative material - Google Patents
One kind is with FeS2-xSexMaterial is the sodium ion capacitor of negative material Download PDFInfo
- Publication number
- CN108172406A CN108172406A CN201711483558.XA CN201711483558A CN108172406A CN 108172406 A CN108172406 A CN 108172406A CN 201711483558 A CN201711483558 A CN 201711483558A CN 108172406 A CN108172406 A CN 108172406A
- Authority
- CN
- China
- Prior art keywords
- fes
- sodium ion
- ion capacitor
- negative
- source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 105
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 66
- 239000003990 capacitor Substances 0.000 title claims abstract description 63
- 239000011149 active material Substances 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 239000006258 conductive agent Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000011669 selenium Substances 0.000 claims description 105
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 60
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 34
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- 239000012046 mixed solvent Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000006230 acetylene black Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 229910052711 selenium Inorganic materials 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000005864 Sulphur Substances 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 229910052603 melanterite Inorganic materials 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 239000011889 copper foil Substances 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 235000011837 pasties Nutrition 0.000 claims description 6
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 5
- 229920001410 Microfiber Polymers 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000003658 microfiber Substances 0.000 claims description 4
- 239000006104 solid solution Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000005030 aluminium foil Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical group [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 10
- 229910052960 marcasite Inorganic materials 0.000 abstract description 10
- 229910052683 pyrite Inorganic materials 0.000 abstract description 10
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003780 insertion Methods 0.000 abstract description 3
- 230000037431 insertion Effects 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 150000003346 selenoethers Chemical class 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 239000008187 granular material Substances 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 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 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- -1 x=0.1-1 Substances 0.000 description 2
- 241000257465 Echinoidea Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- SYHGEUNFJIGTRX-UHFFFAOYSA-N methylenedioxypyrovalerone Chemical compound C=1C=C2OCOC2=CC=1C(=O)C(CCC)N1CCCC1 SYHGEUNFJIGTRX-UHFFFAOYSA-N 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention relates to one kind with FeS2‑xSexMaterial is the sodium ion capacitor of negative material, the sodium ion capacitor includes positive plate, negative plate, diaphragm, electrolyte and shell, and the negative plate is that active material, conductive agent, binding agent are added solvent and are mixed into after slurry and obtained coated on collector after mixing；Active material is FeS in capacitor anode piece2‑xSexMaterial, x=0.1 1.The FeS that sodium ion capacitor anode material of the present invention uses2‑xSexMaterial, compared to FeS2, the peak position of XRD diffraction patterns occurs slightly moving to left, shows that interlamellar spacing increases, be more advantageous to sodium ion insertion abjection；Meanwhile Na+Diffusion faster, electron conduction enhancing, substantially increase the high current charge-discharge ability of sodium ion capacitor, i.e. power-performance, be 172W kg in power density‑1When, energy density is up to 67Wh kg‑1Even if in 2543W kg‑1Under higher power density, energy density still maintains~27Wh kg‑1。
Description
Technical field：
The present invention relates to one kind with FeS2-xSexMaterial is the sodium ion capacitor of negative material, belongs to capacitor technology neck
Domain.
Background technology：
Electrochemical storage device, particularly lithium ion battery are widely used in portable electronic device, electric vehicle, hair
Power station etc. is that current technology develops one of electrochemical energy storing device that is the most ripe, being most widely used, however, lithium is in the earth's crust
In abundance it is very low.With increasingly increase of the new energy industry to lithium ion battery demand, the amount of lithium resource is proposed more
Big demand, and the rarity fast development for greatly limiting lithium ion battery in large-scale energy storage device of lithium resource, and
Lithium ion battery power density is low, also limits it in high power applications.Therefore, find alternative lithium resource, development it is next
Become the problem of extremely urgent for novel high-performance energy storage device.
Sodium metal is in the Ith main group of the periodic table of elements together with lithium metal, has similar row in electrochemical reaction process
For it can be considered to which the lithium in existing lithium-ion energy storage battery is substituted for sodium, and abundance of the sodium metal in the earth's crust will
Far above lithium metal, abundant sodium resource is contained in wide ocean, it is of low cost.Therefore, the height based on sodium ion is developed
The energy storage device of energy density, high power density, it appears particularly important.
Transient metal sulfide/selenides (TMSs) is because of its high specific capacity, the electric conductivity enhanced, moderate M-S
The characteristics such as bond energy, various crystal structure, hence into the people visual field.One of them representative transition metal vulcanization
Object/selenides is FeS2Microballoon under 0.8-3.0V voltage windows, shows splendid cyclical stability (after 20,000 circle of cycle
Remain with 90% capacity) and high rate performance (~170mAh g-1In 20Ag-1)[Energy Environ.Sci.2015,8,
1309.].Similar excellent cycle performance and higher high rate performance are also observed in other sulfide/selenides, such as
FeSe2Microballoon [Adv.Mater.2015,27,3305.]；N doped carbons/CoS nanotubes [Angew Chem.Int.Ed.2016,
55,15831.]；Sea urchin shape CoSe2Nanostructured [Adv.Funct.Mater.2016,26,6728.]；CuS nanosheet/reduction
Graphene oxide (RGO) [ACS Appl.Mater.Interface 2017,9,2309.]；SnS0.5Se0.5Powder [Nano
Energy 2017,41,377.]；MoSe2/ N, P codope rGO [Adv.Funct.Mater.2017,27,1700522.]；VS2
Nanometer sheet [Adv.Mater.2017,29,1702061] etc..However, these sulfide/selenides are undergone in cyclic process
Multiple redox reactions lead to occur serious voltage platform overlapping or slope in constant current charge-discharge curve, will very great Cheng
On degree influence transient metal sulfide/selenides practical application because they neither univoltage platform electrode nor standard
Univoltage platform electrode.Worse, many redox reactions are happened between 1.0-2.0V, this voltage range conduct
Negative material is obviously excessively high and is used as positive electrode too low.
Sodium ion capacitor operation principle is that an electrode is worked by surface adsorption desorption anion, another electrode passes through
Na+Deintercalation works.It is no apparent platform during sodium ion capacitor cycle.
Through retrieval, Transition Metal Sulfur/selenides is applied to sodium ion capacitor, and there is presently no reports.
Invention content：
In view of the deficiencies of the prior art, the present invention provides one kind with FeS2-xSexMaterial is the sodium ion capacitance of negative material
Device, the FeS that sodium ion capacitor anode material of the present invention uses2-xSexMaterial, compared to FeS2, interlamellar spacing increase, Na+Expand
Dissipate rate quickening, electron conduction enhancing；Modified material electrochemical performance is excellent；With FeS2-xSexMaterial is negative material
Obtained sodium ion capacitor is 172W kg in power density-1When, energy density is up to 67Wh kg-1Even if in 2543W
kg-1Under higher power density, energy density still maintains~27Wh kg-1。
Technical scheme is as follows：
One kind is with FeS2-xSexMaterial is the sodium ion capacitor of negative material, and the sodium ion capacitor includes anode
Piece, negative plate, diaphragm, electrolyte and shell, the negative plate are added again after mixing active material, conductive agent, binding agent
Enter solvent, obtained after wearing into slurry coated on collector；Active material is FeS in capacitor anode piece2-xSexMaterial, FeS2- xSexMaterial is graininess, and granularity is 1~3 μm, is solid state inside particle, x=0.1-1, Fe and Se and S mole the sum of ratio
Example be：1:2-4.
According to currently preferred, conductive agent is acetylene black in negative plate, and binding agent is polyvinylidene fluoride (PVDF), molten
Agent be methyl pyrrolidone (NMP), active material：Conductive agent：The mass ratio of binding agent is (60-80):(10-30):(5-15)；
The collector is mostly copper foil, porous titanium net or porous stainless steel mesh.
According to currently preferred, solvent is added after active material, conductive agent, binding agent mixing in negative plate, is worn into
Collector is coated on after slurry, coats and is dried in vacuo after at 50-70 DEG C, is rolled after dry, cuts into pole piece, on unit area
The quality of active material is 1.0-1.5mg cm-2。
According to currently preferred, positive plate is prepared as follows obtaining：Activated carbon, acetylene black, carboxymethyl is fine
The plain sodium of dimension is uniformly mixed, and water is added dropwise, and is milled into paste material, wherein activated carbon, acetylene black, sodium carboxymethylcellulose mass ratio be
8：1：1；Manufactured pasty slurry is coated uniformly on aluminium foil, is coated and is dried in vacuo after at 50-70 DEG C, is rolled, is cut after dry
It cuts and positive plate is made.
According to currently preferred, activated carbon and FeS in negative plate in positive plate2-xSexThe mass ratio control of material exists
(3-6):1。
It is NaClO according to currently preferred, described electrolyte4It is dissolved in tetraethyleneglycol dimethyl ether, NaClO4It is a concentration of
0.5-2mol/L；Diaphragm material is Whatman GF/F glass microfibers.
According to currently preferred, active material FeS2-xSexIt is prepared as follows：
Source of iron, urea are dissolved in the in the mixed solvent of dimethylformamide and ethylene glycol, sulphur source, selenium source is then added in, obtains
Mixed solution；Mixed solution reacts 16~22h at a high temperature of 170~210 DEG C, carried out successively after product centrifugation ethyl alcohol wash, water
It washes, is then dried in vacuo, obtain FeS2-xSexSolid solution microballoon.
It is FeSO according to currently preferred, described source of iron4·7H2O or Fe (NO3)2。
It is sublimed sulfur according to currently preferred, described sulphur source.
It is pure selenium powder according to currently preferred, described selenium source.
According to currently preferred, the addition of source of iron and the molar ratio of urea are：1:4-6.
According to currently preferred, the volume ratio of in the mixed solvent dimethylformamide and ethylene glycol is (10-15)：(15-
20)。
According to currently preferred, the addition of source of iron and the mass volume ratio of mixed solvent are：(0.5-2)：(30-
40)；Unit：mmol/mL.
According to currently preferred, addition and the sulphur source and selenium source integral molar quantity of source of iron are：1:5-7.
According to currently preferred, the molar ratio of sulphur source and selenium source is (1-3)：(1-9).
According to currently preferred, vacuum drying temperature is 50-70 DEG C, drying time 8-16h.
Negative plate slurry of the present invention adds in the amount of solvent and positive plate slurry adds in the amount of water, can stir into slurry
Subject to, it is carried out by the conventional means of this field.
The principle of the present invention：
The active material FeS that sodium ion capacitor anode material of the present invention uses2-xSexWith FeSO4·7H2O, urea, liter
Magnificent sulphur, selenium powder are raw material, with dimethylformamide (DMF), ethylene glycol (EG) for solvent, are made, changed by solvent thermal reaction
S/Se contents successfully obtain the FeS of different content2-xSexSample.The synergistic effect of S/Se solid solution, increases interlamellar spacing and material
The electron conduction of material, contributes to sodium ion to be diffused in the material, substantially increases it as sodium ion capacitor anode
The dynamic performance of material, electrochemistry storage sodium reversible capacity is high, and cycle performance is excellent.
The sodium ion capacitor of the present invention has following outstanding feature：
1st, the FeS that sodium ion capacitor anode material of the present invention uses2-xSexMaterial, compared to FeS2, XRD diffraction flower
Slightly moving to left occurs in the peak position of sample, and shows that interlamellar spacing increases, and is more advantageous to sodium ion insertion abjection；Meanwhile Na+Diffusion is more
Soon, electron conduction enhances, and modified material electrochemical performance is excellent；Sodium ion can quickly material internal be embedded in/
Abjection substantially increases the high current charge-discharge ability of sodium ion capacitor, i.e. power-performance, even if stored energy is in height
Electric current under, also can well be kept.
2nd, the FeS that sodium ion capacitor anode material of the present invention uses2-xSexMaterial, in 2Ag-1Current density under recycle
6000 circles, capacity still maintain 220mAh g-1Attenuation rate is often enclosed down to 0.0044% in left and right.In 40Ag-1High current it is close
Under degree, capacity still maintains 211mAh g-1Left and right.
3rd, sodium ion capacitor of the invention is 172W kg in power density-1When, energy density is up to 67Wh kg-1,
Even if in 2543W kg-1Under higher power density, energy density still maintains~27Wh kg-1。
4th, sodium ion capacitor of the invention is 1Ag in current density-1(current density is based on FeS2-xSexAnd activated carbon
Gross mass) when, cycle 1000 circle, than energy still maintain~34Wh kg-1。
5th, sodium ion of the invention hybridization capacitor system FeS2-xSex//AC has been put forward for the first time sulphur/selenides application
In sodium ion capacitor, it is more for voltage platform quantity during sodium-ion battery to avoid common transition sulfide/selenides
With the predicament of current potential embarrassment, it is proposed that the application new in terms of electrochemical energy storage of sulfide/selenides.
Description of the drawings：
Fig. 1 is the FeS that sodium ion capacitor anode material of the present invention uses2-xSexThe XRD diffraction patterns of material.
Fig. 2 is the FeS that sodium ion capacitor anode material of the present invention uses2-xSexThe stereoscan photograph of material；A is puts
The scanning electron microscope that big multiplying power is 5 μm, b is the scanning electron microscope that enlargement ratio is 1 μm.
Fig. 3 is the FeS that sodium ion capacitor anode material of the present invention uses2-xSexThe element mapping photo of material.
Fig. 4 is the FeS that sodium ion capacitor anode material of the present invention uses2-xSexMaterial is in sodium ion half-cell middle impedance
Figure and density of states figure, wherein, a FeS2-xSexMaterial and FeS2The impedance contrast figure of sample, b FeS2-xSexMaterial and FeS2
The density of states figure of sample.
Fig. 5 is the FeS that sodium ion capacitor anode material of the present invention uses2-xSexElectricity of the material in sodium ion half-cell
Chemical property figure, wherein, a FeS2-xSexMaterial is in 2Ag-1Cycle performance figure under current density, b FeS2-xSexMaterial is not
With the high rate performance figure under current density.
Fig. 6 is the chemical property figure of sodium ion capacitor of the present invention, wherein, a figures are the capacitor of embodiment 1 in difference
Charging and discharging curve figure under current density, b figures are the energy comparison figure (Ragone plots) of capacitor, and c figures are that capacitor exists
1A g-1(current density design is based on FeS at last2-xSexWith the gross mass of activated carbon) under cycle performance figure.
Specific embodiment：
The present invention will be described in more detail with reference to the accompanying drawings and examples.
Raw material in embodiment is commercial products.
Embodiment 1
One kind is with FeS2-xSexMaterial is the sodium ion capacitor of negative material, and the sodium ion capacitor includes anode
Piece, negative plate, diaphragm, electrolyte and shell.
The mass ratio of active material and active material in negative plate is controlled 4 in positive plate:1, electrolyte NaClO4It is molten
In tetraethyleneglycol dimethyl ether, NaClO4A concentration of 1mol/L；Diaphragm material is Whatman GF/F glass microfibers.
Negative plate is to add solvent after mixing active material, conductive agent, binding agent, and copper foil is coated on after wearing into slurry
It obtains；Active material is FeS in capacitor anode piece2-xSexMaterial, conductive agent are acetylene black, and binding agent is polyvinylidene fluoride
(PVDF), solvent be methyl pyrrolidone (NMP), active material：Conductive agent：The mass ratio of binding agent is：70:20:10, cathode
The preparation method of piece is as follows：FeS2-xSexMaterial, acetylene black, polyvinylidene fluoride are dispersed in appropriate methyl pyrrolidone
(NMP) in, hand mill 30min is made pasty slurry, then, slurry is coated uniformly on copper foil, then vacuum is done at 60 DEG C
It is dry；After dried copper foil is rolled, disk is cut into, the active material quality of unit area is 1.0-1.5mg cm-2；
Positive plate is prepared as follows obtaining：Activated carbon, acetylene black, sodium carboxymethylcellulose is taken to be uniformly mixed, is dripped
Add water, be milled into pasty slurry, wherein activated carbon, acetylene black, sodium carboxymethylcellulose mass ratio be 8：1：1；Manufactured paste
Shape slurry is coated uniformly on aluminium foil, is coated and is dried in vacuo after at 60 DEG C, is rolled after dry, is cut into positive plate.
Active material FeS in negative plate2-xSexMaterial is graininess, and granularity is 3 μm, is solid state, x=inside particle
0.4。
FeS2-xSexThe preparation method of material is as follows including step：
(1) by 1mmol FeSO4·7H2O, 5mmol urea is dissolved in the in the mixed solvent of dimethylformamide and ethylene glycol,
Then in the mixed solvent dimethylformamide 15mL, ethylene glycol 20mL add in sublimed sulfur, selenium powder, obtain mixed solution；Sublimed sulfur and
Selenium powder integral molar quantity is 6.5mmol, and the molar ratio of sublimed sulfur and selenium powder is 1:4；
(2) mixed solution is transferred to stainless steel cauldron and is placed in baking oven, reacts 18h at 190 DEG C；
(3) product centrifuges, and is cleaned for several times with ethyl alcohol, water, is placed in the dry 12h of 60 DEG C of vacuum drying chamber, successfully obtains FeS2- xSex(x=0.4) microballoon.FeS obtained2-xSexIt is full particle inside material granule.
Performance test
First, to FeS2-xSexXRD tests are done, diffraction pattern is as shown in Figure 1, Se is adulterated not it can be seen from Fig. 1
There is the object phase for changing sample, all diffraction maximums may both correspond to XRD standard card JCPDS No.42-1340, FeS2-xSexSample
Relative to FeS2XRD diffraction maximums gently towards low angle deviate, showing the introducing of Se makes its spacing of lattice become larger, and is more advantageous to sodium
Ion insertion abjection.To FeS obtained2-xSexSpecimen material does scanning electron microscope analysis, stereoscan photograph as shown in Fig. 2,
As seen from Figure 2, FeS2-xSexThe micron ball that sample is made of little particle.To FeS obtained2-xSexSpecimen material does member
Plain map analysis, element mapping photo are demonstrate,proved again as shown in figure 3, Fe, S, Se Elemental redistribution are uniform it can be seen from Fig. 3
Understand the formation of solid solution.
Electrochemical property test
Sodium ion half-cell performance test：
In order to verify FeS2-xSexThe electric property of material, with FeS2-xSexMaterial is negative material, and sodium piece is reference electrode
With to electrode, sodium ion half-cell is assembled, characterizes chemical property, is prepared by cathode：FeS2-xSexMaterial, acetylene black, poly- inclined two
Vinyl fluoride is dispersed in appropriate methyl pyrrolidone (NMP), and pasty slurry is made in hand mill 30min, then, slurry is equal
It is even to be coated on copper foil, then it is dried in vacuo at 60 DEG C；After dried copper foil is rolled, cathode is made, sodium piece is reference
Electrode and to electrode, Whatman GF/F glass microfibers are diaphragm, 1.0M NaCF3SO3It is dissolved in diethylene glycol dimethyl ether (DGM)
For electrolyte, carry out the glove box (Mikrouna, Super 1220/750/900) full of argon gas is inner.The charge and discharge of battery
Test carries out in blue electric (Land CT-2001A) test system, and battery operation interval is 0.8~3.0V.Fig. 4 a are real
Apply FeS made from example 12-xSexSample and unmodified FeS2The impedance contrast figure of material, 4b are FeS made from embodiment 12- xSexSample and unmodified FeS2The density of states figure of material.FeS it can be seen from Fig. 42-xSexSample is relative to FeS2It is conductive
Property is remarkably reinforced.Fig. 5 a figures are FeS made from embodiment 12-xSexSample is in 2Ag-1Cycle performance figure under current density, b figures
For FeS made from embodiment 12-xSexHigh rate performance figure of the material under different current densities.FeS it can be seen from Fig. 52- xSexThe cycle performance and high rate performance of sample are excellent.
Sodium ion capacitor performance is tested：
Carry out the chemical property under different current densities to the capacitor of embodiment assembling, test result as shown in Figure 6,
Before capacitor assembling, several circles of negative electrode elder generation electrochemical activation.FeS2-xSexThe specific capacity calculating of //AC is based on FeS2-xSex
With the gross mass of AC.Fig. 6 a figures are charging and discharging curve figure of the capacitor of embodiment 1 under different current densities, and b figures are to implement
The energy comparison figure (Ragone plots) of the capacitor of example 1, c figures are the capacitor of embodiment 1 in 1Ag-1(current density calculates
It is based on FeS2-xSexWith the gross mass of activated carbon) under cycle performance figure..From fig. 6, it can be seen that it is 172W in power density
kg-1When, energy density is up to 67Wh kg-1Even if in 2543W kg-1Under higher power density, energy density is still tieed up
It holds in~27Wh kg-1.In addition, in 1Ag-1Under high current density, 1000 circle of cycle still maintains~34Wh kg than energy-1。
Embodiment 2
One kind is with FeS2-xSexMaterial is the sodium ion capacitor of negative material, and shown in embodiment 1, difference exists
In：
FeS2-xSexThe preparation method of material is as follows including step：
(1) by 1mmol FeSO4·7H2O, 5mmol urea is dissolved in the in the mixed solvent of dimethylformamide and ethylene glycol,
Then in the mixed solvent dimethylformamide 15mL, ethylene glycol 20mL add in sublimed sulfur, selenium powder, obtain mixed solution；Sublimed sulfur and
Selenium powder integral molar quantity is 6.5mmol, and the molar ratio of sublimed sulfur and selenium powder is 1:9；
(2) mixed solution is transferred to stainless steel cauldron and is placed in baking oven, reacts 22h at 170 DEG C；
(3) product centrifuges, and is cleaned for several times with ethyl alcohol, water, is placed in the dry 16h of 50 DEG C of vacuum drying chamber, successfully obtains FeS2- xSex(x=0.2) microballoon.FeS obtained2-xSexIt is full particle inside material granule.
Embodiment 3
One kind is with FeS2-xSexMaterial is the sodium ion capacitor of negative material, and shown in embodiment 1, difference exists
In：
FeS2-xSexThe preparation method of material is as follows including step：
(1) by 1mmol FeSO4·7H2O, 5mmol urea is dissolved in the in the mixed solvent of dimethylformamide and ethylene glycol,
Then in the mixed solvent dimethylformamide 15mL, ethylene glycol 20mL add in sublimed sulfur, selenium powder, obtain mixed solution；Sublimed sulfur and
Selenium powder integral molar quantity is 6.5mmol, and the molar ratio of sublimed sulfur and selenium powder is 1:9；
(2) mixed solution is transferred to stainless steel cauldron and is placed in baking oven, reacts 20h at 180 DEG C；
(3) product centrifuges, and is cleaned for several times with ethyl alcohol, water, is placed in the dry 14h of 52 DEG C of vacuum drying chamber, successfully obtains FeS2- xSex(x=0.2) microballoon.FeS obtained2-xSexIt is full particle inside material granule.
Embodiment 4
One kind is with FeS2-xSexMaterial is the sodium ion capacitor of negative material, and shown in embodiment 1, difference exists
In：
FeS2-xSexThe preparation method of material is as follows including step：
(1) by 1mmol FeSO4·7H2O, 5mmol urea is dissolved in the in the mixed solvent of dimethylformamide and ethylene glycol,
Then in the mixed solvent dimethylformamide 15mL, ethylene glycol 20mL add in sublimed sulfur, selenium powder, obtain mixed solution；Sublimed sulfur and
Selenium powder integral molar quantity is 6.5mmol, and the molar ratio of sublimed sulfur and selenium powder is 1:4；
(2) mixed solution is transferred to stainless steel cauldron and is placed in baking oven, reacts 16h at 200 DEG C；
(3) product centrifuges, and is cleaned for several times with ethyl alcohol, water, is placed in the dry 12h of 60 DEG C of vacuum drying chamber, successfully obtains FeS2- xSex(x=0.4) microballoon.FeS obtained2-xSexIt is full particle inside material granule.
Embodiment 5
One kind is with FeS2-xSexMaterial is the sodium ion capacitor of negative material, and shown in embodiment 1, difference exists
In：
FeS2-xSexThe preparation method of material is as follows including step：
(1) by 1mmol FeSO4·7H2O, 5mmol urea is dissolved in the in the mixed solvent of dimethylformamide and ethylene glycol,
Then in the mixed solvent dimethylformamide 15mL, ethylene glycol 20mL add in sublimed sulfur, selenium powder, obtain mixed solution；Sublimed sulfur and
Selenium powder integral molar quantity is 6.5mmol, and the molar ratio of sublimed sulfur and selenium powder is 3:7；
(2) mixed solution is transferred to stainless steel cauldron and is placed in baking oven, reacts 17h at 200 DEG C；
(3) product centrifuges, and is cleaned for several times with ethyl alcohol, water, is placed in the dry 12h of 60 DEG C of vacuum drying chamber, successfully obtains FeS2- xSex(x=0.4) microballoon.FeS obtained2-xSexIt is full particle inside material granule.
Embodiment 6
One kind is with FeS2-xSexMaterial is the sodium ion capacitor of negative material, and shown in embodiment 1, difference exists
In：
FeS2-xSexThe preparation method of material is as follows including step：
(1) by 1mmol FeSO4·7H2O, 5mmol urea is dissolved in the in the mixed solvent of dimethylformamide and ethylene glycol,
Then in the mixed solvent dimethylformamide 15mL, ethylene glycol 20mL add in sublimed sulfur, selenium powder, obtain mixed solution；Sublimed sulfur and
Selenium powder integral molar quantity is 6.5mmol, and the molar ratio of sublimed sulfur and selenium powder is 2:3；
(2) mixed solution is transferred to stainless steel cauldron and is placed in baking oven, reacts 16h at 210 DEG C；
(3) product centrifuges, and is cleaned for several times with ethyl alcohol, water, is placed in the dry 12h of 60 DEG C of vacuum drying chamber, successfully obtains FeS2- xSex(x=0.8) microballoon.FeS obtained2-xSexIt is full particle inside material granule.
Embodiment 7
One kind is with FeS2-xSexMaterial is the sodium ion capacitor of negative material, and shown in embodiment 1, difference exists
In：
FeS2-xSexThe preparation method of material is as follows including step：
(1) by 1mmol FeSO4·7H2O, 5mmol urea is dissolved in the in the mixed solvent of dimethylformamide and ethylene glycol,
Then in the mixed solvent dimethylformamide 15mL, ethylene glycol 20mL add in sublimed sulfur, selenium powder, obtain mixed solution；Sublimed sulfur and
Selenium powder integral molar quantity is 6.5mmol, and the molar ratio of sublimed sulfur and selenium powder is 1:1；
(2) mixed solution is transferred to stainless steel cauldron and is placed in baking oven, reacts 16h at 210 DEG C；
(3) product centrifuges, and is cleaned for several times with ethyl alcohol, water, is placed in the dry 10h of 70 DEG C of vacuum drying chamber, successfully obtains FeS2- xSex(x=1) microballoon.FeS obtained2-xSexIt is full particle inside material granule.
Claims (10)
1. one kind is with FeS2-xSexMaterial be negative material sodium ion capacitor, the sodium ion capacitor include positive plate,
Negative plate, diaphragm, electrolyte and shell, the negative plate be will active material, conductive agent, binding agent mix after add it is molten
Agent obtains after wearing into slurry coated on collector；Active material is FeS in capacitor anode piece2-xSexMaterial, FeS2-xSexMaterial
Expect for graininess, granularity is 1~3 μm, inside particle for solid state, x=0.1-1, Fe and Se and S mole the sum of ratio be：
1:2-4。
It is 2. according to claim 1 with FeS2-xSexMaterial is the sodium ion capacitor of negative material, which is characterized in that negative
Conductive agent is acetylene black in pole piece, and binding agent is polyvinylidene fluoride (PVDF), and solvent is methyl pyrrolidone (NMP), active
Material：Conductive agent：The mass ratio of binding agent is (60-80):(10-30):(5-15)；The collector is mostly copper foil, porous
Titanium net or porous stainless steel mesh.
It is 3. according to claim 1 with FeS2-xSexMaterial is the sodium ion capacitor of negative material, which is characterized in that negative
Add solvent after active material in pole piece, conductive agent, binding agent mixing, collector be coated on after wearing into slurry, coat after
It is dried in vacuo at 50-70 DEG C, is rolled after dry, cut into pole piece, the quality of active material is 1.0-1.5mg on unit area
cm-2
It is 4. according to claim 1 with FeS2-xSexMaterial is the sodium ion capacitor of negative material, which is characterized in that just
Pole piece is prepared as follows obtaining：Activated carbon, acetylene black, sodium carboxymethylcellulose is taken to be uniformly mixed, water is added dropwise, is milled into
Pasty slurry, wherein activated carbon, acetylene black, sodium carboxymethylcellulose mass ratio be 8：1：1；Manufactured pasty slurry uniformly applies
It overlays on aluminium foil, coats and be dried in vacuo after at 50-70 DEG C, rolled after dry, be cut into positive plate.
5. according to claim 2 or 4 with FeS2-xSexMaterial is the sodium ion capacitor of negative material, which is characterized in that
Activated carbon and FeS in negative plate in positive plate2-xSexThe mass ratio of material is controlled at (3-6):1；The electrolyte is NaClO4
It is dissolved in tetraethyleneglycol dimethyl ether, NaClO4A concentration of 0.5-2mol/L；Diaphragm material is Whatman GF/F glass microfibers.
It is 6. according to claim 1 with FeS2-xSexMaterial is the sodium ion capacitor of negative material, which is characterized in that living
Property material FeS2-xSexIt is prepared as follows：
Source of iron, urea are dissolved in the in the mixed solvent of dimethylformamide and ethylene glycol, sulphur source, selenium source is then added in, must mix
Solution；Mixed solution reacts 16~22h at a high temperature of 170~210 DEG C, and carrying out ethyl alcohol successively after product centrifugation washes, washes, so
After be dried in vacuo, obtain FeS2-xSexSolid solution microballoon.
It is 7. according to claim 6 with FeS2-xSexMaterial is the sodium ion capacitor of negative material, which is characterized in that institute
The source of iron stated is FeSO4·7H2O or Fe (NO3)2, the sulphur source is sublimed sulfur, and the selenium source is pure selenium powder.
It is 8. according to claim 6 with FeS2-xSexMaterial is the sodium ion capacitor of negative material, which is characterized in that iron
The addition in source and the molar ratio of urea are：1：The volume ratio of 4-6, in the mixed solvent dimethylformamide and ethylene glycol is (10-
15)：(15-20).
It is 9. according to claim 6 with FeS2-xSexMaterial is the sodium ion capacitor of negative material, which is characterized in that iron
The addition in source and the mass volume ratio of mixed solvent are：(0.5-2)：(30-40)；Unit：Mmol/mL, the addition of source of iron
It is with sulphur source and selenium source integral molar quantity：1:5-7.
It is 10. according to claim 6 with FeS2-xSexMaterial is the sodium ion capacitor of negative material, which is characterized in that sulphur
The molar ratio of source and selenium source is (1-3)：(1-9), vacuum drying temperature are 50-70 DEG C, drying time 8-16h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711483558.XA CN108172406B (en) | 2017-12-29 | 2017-12-29 | FeS is used as a catalyst2-xSexSodium ion capacitor with negative electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711483558.XA CN108172406B (en) | 2017-12-29 | 2017-12-29 | FeS is used as a catalyst2-xSexSodium ion capacitor with negative electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108172406A true CN108172406A (en) | 2018-06-15 |
| CN108172406B CN108172406B (en) | 2020-04-21 |
Family
ID=62516209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711483558.XA Expired - Fee Related CN108172406B (en) | 2017-12-29 | 2017-12-29 | FeS is used as a catalyst2-xSexSodium ion capacitor with negative electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108172406B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109437123A (en) * | 2018-10-16 | 2019-03-08 | 中山高容新能源科技有限公司 | The ferrous disulfide carbon coating composite material and preparation method and application that selenium mixes |
| CN110280205A (en) * | 2019-06-26 | 2019-09-27 | 江西理工大学 | A kind of magnetism selenium doping iron-sulfur complex and its preparation method and application |
| CN112960653A (en) * | 2021-01-29 | 2021-06-15 | 青岛科技大学 | Sulfur-doped iron selenide nanorod material and preparation method and application thereof |
| CN114725353A (en) * | 2022-04-29 | 2022-07-08 | 长江师范学院 | Novel metal chalcogenide solid solution electrode material and preparation method and application thereof |
| WO2023045125A1 (en) * | 2021-09-24 | 2023-03-30 | 中国科学院深圳先进技术研究院 | Negative electrode material and preparation method therefor, and sodium-ion battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080118835A1 (en) * | 2006-11-20 | 2008-05-22 | So-Hyun Hur | Rechargeable lithium battery |
| CN107195876A (en) * | 2017-04-27 | 2017-09-22 | 华中科技大学 | The preparation method and sodium-ion battery of a kind of Nanoscale Iron selenium sulfide |
| CN107452951A (en) * | 2017-08-11 | 2017-12-08 | 西南大学 | XS2@YSe2The preparation method of the anode material of lithium-ion battery of core shell structure |
-
2017
- 2017-12-29 CN CN201711483558.XA patent/CN108172406B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080118835A1 (en) * | 2006-11-20 | 2008-05-22 | So-Hyun Hur | Rechargeable lithium battery |
| CN107195876A (en) * | 2017-04-27 | 2017-09-22 | 华中科技大学 | The preparation method and sodium-ion battery of a kind of Nanoscale Iron selenium sulfide |
| CN107452951A (en) * | 2017-08-11 | 2017-12-08 | 西南大学 | XS2@YSe2The preparation method of the anode material of lithium-ion battery of core shell structure |
Non-Patent Citations (1)
| Title |
|---|
| JIABIN LIU ET AL: "Facile synthesis and electrochemical properties of Fe2SeS for lithium ion", 《JOURNAL OF POWER SOURCES》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109437123A (en) * | 2018-10-16 | 2019-03-08 | 中山高容新能源科技有限公司 | The ferrous disulfide carbon coating composite material and preparation method and application that selenium mixes |
| CN109437123B (en) * | 2018-10-16 | 2022-05-31 | 中山高容新能源科技有限公司 | Selenium-doped ferrous disulfide carbon-coated composite material and preparation method and application thereof |
| CN110280205A (en) * | 2019-06-26 | 2019-09-27 | 江西理工大学 | A kind of magnetism selenium doping iron-sulfur complex and its preparation method and application |
| CN110280205B (en) * | 2019-06-26 | 2021-12-21 | 江西理工大学 | Magnetic selenium-doped iron-sulfur compound and preparation method and application thereof |
| CN112960653A (en) * | 2021-01-29 | 2021-06-15 | 青岛科技大学 | Sulfur-doped iron selenide nanorod material and preparation method and application thereof |
| CN112960653B (en) * | 2021-01-29 | 2022-07-22 | 青岛科技大学 | Sulfur-doped iron selenide nanorod material as well as preparation method and application thereof |
| WO2023045125A1 (en) * | 2021-09-24 | 2023-03-30 | 中国科学院深圳先进技术研究院 | Negative electrode material and preparation method therefor, and sodium-ion battery |
| CN114725353A (en) * | 2022-04-29 | 2022-07-08 | 长江师范学院 | Novel metal chalcogenide solid solution electrode material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108172406B (en) | 2020-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhuang et al. | Hydrothermal synthesis of mesoporous MoO2 nanospheres as sulfur matrix for lithium sulfur battery | |
| Yuan et al. | Polysulfides anchoring and enhanced electrochemical kinetics of 3D flower-like FeS/carbon assembly materials for lithium-sulfur battery | |
| Xu et al. | Tri-functionalized polypropylene separator by rGO/MoO 2 composite for high-performance lithium–sulfur batteries | |
| Li et al. | High-performance lithium-sulfur batteries with a carbonized bacterial cellulose/TiO2 modified separator | |
| CN108172406A (en) | One kind is with FeS2-xSexMaterial is the sodium ion capacitor of negative material | |
| Wang et al. | Novel functional separator with self-assembled MnO2 layer via a simple and fast method in lithium-sulfur battery | |
| Li et al. | Hierarchical porous carbon aerogels with VN modification as cathode matrix for high performance lithium-sulfur batteries | |
| CN108269978B (en) | Quantum dot/carbon tube sulfur-carrying composite cathode material and preparation method and application thereof | |
| CN106252659A (en) | Integrated flexible thin film lithium sulfur or lithium ion battery cell, battery and preparation method | |
| Jiang et al. | A tin disulfide nanosheet wrapped with interconnected carbon nanotube networks for application of lithium sulfur batteries | |
| Mao et al. | High loading cotton cellulose-based aerogel self-standing electrode for Li-S batteries | |
| CN111517374B (en) | Fe7S8Preparation method of/C composite material | |
| Zhang et al. | Superior cycling life of Li–S batteries with high sulfur loading enabled by a bifunctional layered-MoO3 cathode | |
| CN105514378A (en) | Lithium-sulfur battery positive-pole composite material with imitated cellular structure and preparation method thereof | |
| Wu et al. | Encapsulation of sulfur cathodes by sericin-derived carbon/Co3O4 hollow microspheres for the long-term cyclability of lithium-sulfur batteries | |
| CN106058151B (en) | Carbon nanotube/nano sulphur/polyaniline composite electrode, preparation method and application | |
| Zhao et al. | Synergistically enhanced sodium/potassium ion storage performance of SnSb alloy particles confined in three-dimensional carbon framework | |
| CN107732203B (en) | Preparation method of nano cerium dioxide/graphene/sulfur composite material | |
| CN105883940A (en) | Preparation method of block NiS2 and application of block NiS2 to sodium-ion battery | |
| CN108258209A (en) | A kind of carbide/carbon nano tube/graphene carries sulphur composite material and preparation method and application | |
| Wang et al. | Fabrication of CuCo2S4 hollow sphere@ N/S doped graphene composites as high performance anode materials for lithium ion batteries | |
| Song et al. | Effective polysulfide adsorption and catalysis by polyoxometalate contributing to high-performance Li–S batteries | |
| CN109742439A (en) | A kind of novel lithium-sulfur cell porous interlayer material, preparation method and application | |
| CN107978736B (en) | Metal alloy/carbon tube/graphene sulfur-loaded composite cathode material and preparation method and application thereof | |
| Fang et al. | MoS2/G interlayer as a polysulfide immobilization apparatus for high-performance lithium–sulfur batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200421 Termination date: 20201229 |