CN102214816B - Grapheme/WS2 nanocomposite electrode of lithium ion battery and manufacturing method thereof - Google Patents
Grapheme/WS2 nanocomposite electrode of lithium ion battery and manufacturing method thereof Download PDFInfo
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000002114 nanocomposite Substances 0.000 title abstract description 18
- 238000004519 manufacturing process Methods 0.000 title abstract 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 178
- 239000002086 nanomaterial Substances 0.000 claims abstract description 79
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 65
- 239000010439 graphite Substances 0.000 claims abstract description 65
- 239000011149 active material Substances 0.000 claims abstract description 27
- 239000006230 acetylene black Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 80
- 239000002131 composite material Substances 0.000 claims description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 23
- 238000005119 centrifugation Methods 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000011889 copper foil Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims 1
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 25
- 238000000034 method Methods 0.000 abstract description 24
- 239000000126 substance Substances 0.000 abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052744 lithium Inorganic materials 0.000 abstract description 18
- 238000003860 storage Methods 0.000 abstract description 15
- 230000002441 reversible effect Effects 0.000 abstract description 11
- 239000002135 nanosheet Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000002033 PVDF binder Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract 1
- 230000005518 electrochemistry Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000002055 nanoplate Substances 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a grapheme/WS2 nanocomposite electrode of a lithium ion battery and a manufacturing method thereof. The electrode comprise 75-85% of nanocomposite active materials consisting of grapheme nano-sheets and WS2, 5-10% of acetylene black and 10% of polyvinylidene fluoride in percentage by mass, wherein the amount-of-material rate of the grapheme nano-sheets to the WS2 nano materials in the nanocomposite active materials is (1:1)-(4:1). The manufacturing method of the electrode comprises the following steps: using a chemical oxidation method to manufacture graphite oxide nano-sheets by taking graphite as a raw material; under the existence of the graphite oxide nano-sheets, synthesizing by using a hydrothermal in-situ reduction method so as to obtain the grapheme nano-sheets/WS2 nanocomposite; and manufacturing the electrode by taking the grapheme nano-sheets/WS2 nanocomposite as the active material. The electrode has the advantages of high electrochemical lithium storage reversible capacity and stable circulation property, and can be widely applied to next-generation lithium ion batteries.
Description
The present invention relates to lithium ion cell electrode and preparation method thereof, especially use graphene nanometer sheet and WS
2the high power capacity that composite material is prepared as electroactive substance and the lithium ion cell electrode of stable cycle performance, belong to mechanism of new electrochemical power sources and new energy materials field.
Background technology
Lithium ion battery has the excellent properties such as specific energy is high, memory-less effect, environmental friendliness, has been widely used in the Portable movable electrical equipment such as mobile phone and notebook computer.As electrokinetic cell, lithium ion battery is also with a wide range of applications on electric bicycle and electric automobile.The negative material of lithium ion battery mainly adopts graphite material (as: graphite microspheres, natural modified graphite and Delanium etc.) at present, these graphite materials have good stable circulation performance, but its capacity is lower, the theoretical capacity of graphite is 372mAh/g.A new generation's lithium ion battery is had higher requirement to the capacity of electrode material and stable circulation performance, not only requires negative material to have high electrochemistry capacitance, and has good stable circulation performance.
Graphene nanometer sheet has the performances such as physics, chemistry and mechanics of numerous uniquenesses with its unique two-dimensional nano chip architecture, have important scientific research meaning and application prospect widely.The finder of grapheme material obtains the Nobel Prize in 2010 and has excited especially the very big interest of people to grapheme material research.Recently, graphene nanometer sheet and composite material thereof synthetic and getting the attention as the research of lithium ion battery negative material.Lithium can be store in the both sides of the bright graphene nanometer sheet of theoretical computational chart, and its theoretical capacity is 744mAh/g, is the twice of graphite theoretical capacity (372mAh/g).Yoo etc. [Nano Letters, 2008,8 (8): 2277-2282] studies show that Graphene has higher electrochemical reversible storage lithium capacity (540mAh/g), Graphene and carbon nano-tube or C
60the electrochemistry storage lithium capacity of compound composite material is respectively 730 and 784mAh/g.But the cycle performance of some bibliographical information Graphenes and composite electrode thereof need to improve, cycle performance is not good enough to be likely due to the unstable of graphene nano chip architecture in the inappropriate arrangement of graphene nanometer sheet and charge and discharge process or to reunite.
On the other hand, WS
2the typical layered structure with similar graphite.WS
2layer structure is the layer structure of sandwich, is very strong covalent bond (S-W-S) in its layer, and interlayer is weak Van der Waals force, easily peels off between layers.WS
2weak interlaminar action power and larger interlamellar spacing allow to be reacted at its interlayer and introduced external atom or molecule by insertion.Such characteristic makes WS
2material can be used as the material of main part that inserts reaction.Therefore, WS
2it is the electrode material of a kind of rising electrochemical lithium storage for heavy-duty battery and electrochemistry storage magnesium.Seo etc. [Seo JW, Jun YW, Park SW, et a., Angew.Chem.Int.Ed., 2007,46:8828-8831] are that precursor has synthesized WS with tungsten oxide nanometer rod
2nanometer sheet, its electrochemistry storage lithium capacity is 377mAh/g, but 30 later its capability retentions of circulation have only kept 64% of initial capacity, and its capacity and cycle performance all remain to be further improved.In addition, although WS
2lamellar compound is a kind of up-and-coming electrochemical lithium storage electrode material, but as the electrode material of electrochemical reaction, WS
2electric conductivity poor.
Due to graphene nanometer sheet and WS
2nano material all has good electrochemistry storage lithium performance, have good application prospect, but their electrochemistry storage lithium capacity and stable circulation performance need further raising as lithium ion battery negative material of new generation.If by graphene nanometer sheet and WS
2the compound composite nano materials that obtains of nano material, can utilize both advantages and the electrochemistry storage lithium performance of synergy reinforced composite.The high conduction performance of graphene nanometer sheet can further improve the electric conductivity of composite material, is conducive to the electronics transmission in electrochemical electrode course of reaction, the chemical property of reinforced composite; The superpower mechanical property performance of Graphene is conducive to keep the stable of electrode structure in charge and discharge process, and composite material also can suppress the reunion of graphene nanometer sheet, therefore greatly improves its stable circulation performance.Graphene nanometer sheet and WS in addition
2nano material is compound, large ∏ key and the WS of graphene nanometer sheet
2the interaction of Electronic Structure, can form the layer structure between a kind of new different material, and its interlamellar spacing is greater than the interlamellar spacing of graphite, is less than WS
2interlamellar spacing, the electrochemistry storage lithium performance of the suitable favourable reinforced composite of interlamellar spacing structure.
But, up to the present, with graphene nanometer sheet/WS
2the lithium ion cell electrode that nano composite material has high power capacity and high stable circulation performance as electroactive substance preparation yet there are no open report.
The application of biological micromolecule in nano material is synthetic recently obtained people's extensive concern.Cys contains a plurality of functional group (as: NH
2,-COOH and-SH), these functional groups can provide coordination atom and metal cation to form coordinate bond.Cys has obtained application in synthetic transient metal sulfide nano material.Document [Zhang B, Ye XC, Hou WY, Zhao Y, Xie Y.Biomolecule-assistedsynthesis and electrochemical hydrogen storage of Bi
2s
3flowerlike patterns withwell-aligned nanorods.Journal of Physical Chemistry B, 2006,110 (18) 8978～8985] with Cys, synthesized the Bi of floriform appearance
2s
3nano structural material.But up to the present, application Cys is assisted synthesizing graphite alkene and WS
2composite nano materials the method for preparing lithium ion cell electrode yet there are no open report.
Summary of the invention
The object of the present invention is to provide a kind of silicon/carbon/graphite in lithium ion batteries alkene/WS
2composite nano materials electrode and preparation method, the active material that it is characterized in that this electrode is graphene nanometer sheet and WS
2composite nano materials, all the other are acetylene black and Kynoar, the mass percentage content of each component is: composite nano materials active material 75-85%, acetylene black 5-10%, Kynoar 10%, wherein, graphene nanometer sheet and WS in composite nano materials active material
2the ratio of the amount of nano material is 1: 1～4: 1.
A kind of silicon/carbon/graphite in lithium ion batteries alkene/WS provided by the invention
2composite nano materials electrode, is characterized in that preparation method comprises the following steps:
1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, 0.015-0.072g graphite powder is distributed in the 20-25mL concentrated sulfuric acid, adds KMnO under stirring
4, institute adds KMnO
4quality be graphite 3-4 doubly, stir 30-60 minute, temperature rises to 30-35 ℃ of left and right, adds 40-50ml deionized water, stirs 20-30 minute, adds the H of 10-15ml mass concentration 30%
2o
2, stir 5-20 minute, through centrifugation, with obtaining graphite oxide nanometer sheet after mass concentration 5%HCl solution, deionized water and acetone cyclic washing;
2) wolframic acid is dissolved in to the solution that forms 0.02～0.07M in deionized water, adding Cys is sulphur source and reducing agent, Cys is 5: 1～12: 1 with the ratio of the amount of wolframic acid, again will be by the 1st) the preparation-obtained graphite oxide nanometer sheet of step adds in this solution, the 1st) step graphite raw material amount of substance used is 1: 1～4: 1 with the ratio of the amount of wolframic acid, ultrasonic processing 1-2h, graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, this mixture is proceeded to hydrothermal reaction kettle and sealed, at 250-290 ℃ of reaction 20-36h, the product centrifugation obtaining, and with deionized water and absolute ethanol washing, dry, finally at 90%N
2-10%H
2in atmosphere, 800-1000 ℃ of heat treatment 2h, obtains graphene nanometer sheet and WS
2composite nano materials.
3) by graphene nanometer sheet/WS
2composite nano materials is as the active material of electrode, under agitation fully mix the uniform pastel of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black and mass concentration 5%, each constituent mass percentage is: nano composite material active material 75-85%, acetylene black 5-10%, Kynoar 10%, this pastel is coated onto equably on the Copper Foil of collector, and dry, roll extrusion obtains electrode.
Method of the present invention has reaction condition gentleness and the simple feature of technique.Graphene nanometer sheet and WS for the inventive method
2the electrode of the lithium ion battery prepared of the composite nano materials active material that is electrode there is high electrochemistry storage lithium capacity and overstable cycle performance.
Method of the present invention has advantages of following outstanding compared with the prior art:
(1) due to graphene nanometer sheet, there is the excellent properties such as high specific area, superpower mechanical property, high conduction and heat conduction, therefore, graphene nanometer sheet and WS for the present invention
2composite nano materials prepare electrode and be conducive to the electronics transmission in electrode process, strengthen the chemical property of composite nano materials electrode.In addition, due to large ∏ key and the WS of graphene nanometer sheet
2the interaction of Electronic Structure, graphene nanometer sheet and WS
2nano material compound, can form the electronic structure between a kind of new different material, and the electrons height delocalization of participation role, is conducive to the quick transmission of electronics in electrochemical reaction process.This graphene nanometer sheet and WS
2composite nano materials as electrode material electrochemistry storage lithium, can significantly strengthen its chemical property.
(2) in course of reaction of the present invention, stannic oxide/graphene nano sheet in-situ reducing becomes graphene nanometer sheet, and reacts the Wolfram disulfide nano Material cladding formation composite material forming with Situ Hydrothermal.Its advantage is: graphite oxide nanometer sheet contains abundant oxygen-containing functional group (as: hydroxyl, carbonyl and carboxyl etc.), in hydro-thermal reaction solution, after ultrasonic dispersion, no longer easily again reunited or be deposited in together, and the functional group on graphite oxide surface can be adsorbed on tungstate radicle the surface of graphite oxide nanometer sheet by complexing, in reproducibility hydrothermal reaction process, can be that generated in-situ graphene nanometer sheet and Wolfram disulfide nano material height are evenly compound, heat treatment obtains the composite nano materials of graphene nanometer sheet and tungsten disulfide.
(3) Cys contains a plurality of functional group (as: NH
2,-COOH and-SH), these functional groups can provide coordination atom and ion to form coordinate bond.Therefore, Cys can with solution in tungstate radicle Zhong center tungsten ion form coordination.While is due to the existence of stannic oxide/graphene nano sheet in solution, just formed the coordination mode of stannic oxide/graphene nano sheet-tungstate radicle-Cys, in reproducibility hydrothermal reaction process, can be evenly compound nano material of generated in-situ graphene nanometer sheet and Wolfram disulfide nano material height, heat treatment obtains the composite nano materials of graphene nanometer sheet and tungsten disulfide.
(4) existence of graphene nanometer sheet in the intermediate product in preparation process, can suppress the excessive crystal growth of tungsten disulfide in heat treatment process and reunite, obtain the less Wolfram disulfide nano material of the lower and number of plies of relative crystallinity and the composite nano materials of graphene nanometer sheet, such composite nano materials has high electrochemistry and stores lithium capacity and overstable cycle performance.
(3) method of the present invention has reaction condition gentleness, and technique is simple, the advantage of the high and favorable reproducibility of productive rate.Due to graphene nanometer sheet and WS
2synergy, graphene nanometer sheet and WS for the present invention
2the electrode of the lithium ion battery prepared of the composite nano materials active material that is electrode there is high electrochemistry storage lithium capacity and overstable cycle performance.
Embodiment
Embodiment 1:
1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, 1.25mmol (0.015g) graphite powder is distributed in the 20mL concentrated sulfuric acid, adds 0.03g KMnO under stirring
4, institute adds KMnO
4quality be 3 times of graphite, stir 30 minutes, temperature rises to 30 ℃ of left and right, adds 45ml deionized water, stirs 20 minutes, adds the H of 10ml mass concentration 30%
2o
2, stir 5 minutes, through centrifugation, with obtaining graphite oxide nanometer sheet after mass concentration 5%HCl solution, deionized water and acetone cyclic washing;
2) 1.25mmol wolframic acid is dissolved in 63ml deionized water, form the solution of 0.02M, add the Cys of 6.25mmol to stir, Cys is 5.0: 1 with the ratio of the amount of wolframic acid, then by the 1st) the prepared graphite oxide nanometer sheet of graphite of 1.25mmol for step (0.015g) adds in this solution, in the amount of substance of graphite raw material used and solution, wolframic acid amount ratio is 1: 1, ultrasonic processing 1.0h, graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, then this mixture is transferred in hydrothermal reaction kettle, at 26 ℃, hydro-thermal reaction is 24 hours, naturally cooling, centrifugation, with deionized water, fully wash rear collection dry, finally at 90%N
2-10%H
2in atmosphere, 800 ℃ of heat treatment 2h, obtain graphene nanometer sheet and WS
2composite nano materials, graphene nanometer sheet and WS in composite nano materials
2the ratio of amount be 1: 1.SEM, EDS and XRD analysis show that composite material is graphene nanometer sheet and WS
2composite nano materials.
3) with the above-mentioned graphene nanometer sheet making and WS
2composite nano materials as electroactive substance, prepare electrode, nano composite material active material and acetylene black are under agitation fully mixed with the 1-METHYLPYRROLIDONE solution of the Kynoar of mass concentration 5%, the uniform pastel of furnishing, this pastel is coated onto equably on the Copper Foil of collector, then vacuumize 12h at 120 ℃, obtains electrode through roll extrusion after taking-up again.Wherein the mass percentage content of each component is: nano composite material active material 80%, acetylene black 10%, Kynoar 10%.
4) with lithium paper tinsel as to electrode and reference electrode, electrolyte is 1.0M LiPF
6eC/DMC solution (1: 1in volume), barrier film is polypropylene film (Celguard-2300), is assembled into test battery in being full of the suitcase of argon gas.The test of battery constant current charge-discharge is carried out on programme controlled auto charge and discharge instrument, charging and discharging currents density 100mA/g, voltage range 0.01～3.00V.
As a comparison, 1.25mmol wolframic acid is dissolved in 63ml deionized water, the solution that forms 0.02M, adds the Cys of 6.25mmol to stir, and Cys is 5.0: 1 with the ratio of the amount of wolframic acid, this solution is transferred in hydrothermal reaction kettle, at 260 ℃, hydro-thermal reaction is 24 hours, naturally cooling, centrifugation, with deionized water, fully wash rear collection dry, finally at 90%N
2-10%H
2in atmosphere, 800 ℃ of heat treatment 2h, obtain WS
2nano material.Use resulting WS
2nano material by above-mentioned same method preparation work electrode, and is tested its electrochemistry doff lithium reversible capacity and cycle performance by above-mentioned same method as electroactive substance.
Electrochemical results shows: with synthetic graphene nanometer sheet and the WS of embodiment 1
2the electrode prepared of composite nano materials, its initial reversible capacity reaches 743mAh/g, after circulation 100 times, capacity is 731mAh/g.And with Hydrothermal Synthesis WS
2the nano material electrode that is active material, its initial reversible capacity is up to 567mAh/g, but its capacity loss are to 322mAh/g after circulation 100 times.Illustrate with graphene nanometer sheet and WS
2the electrode prepared of composite nano materials compare WS
2nano material electrode has the stable circulation performance of higher specific capacity and Geng Gao.
Embodiment 2:
1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, 2.5mmol (0.03g) graphite powder is distributed in the 25mL concentrated sulfuric acid, adds KMnO under stirring
4, institute adds KMnO
4quality be 4 times of graphite, stir 40 minutes, temperature rises to 33 ℃ of left and right, adds 50ml deionized water, stirs 25 minutes, adds the H of 12ml mass concentration 30%
2o
2, stir 5-10 minute, through centrifugation, with obtaining graphite oxide nanometer sheet after mass concentration 5%HCl solution, deionized water and acetone cyclic washing;
2) 1.25mmol wolframic acid is dissolved in 63ml deionized water, form the solution of 0.02M, add the Cys of 7.5mmol to stir, wherein Cys is 6: 1 with the ratio of the amount of wolframic acid, then by the 1st) the prepared graphite oxide nanometer sheet of graphite of 2.5mmol for step (0.03g) adds in this solution, in the amount of substance of graphite raw material used and solution, wolframic acid amount ratio is 2: 1, ultrasonic processing 1.5h, graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, then this mixture is transferred in hydrothermal reaction kettle, at 270 ℃, hydro-thermal reaction is 28 hours, naturally cooling, centrifugation, with deionized water, fully wash rear collection dry, finally at 90%N
2-10%H
2in atmosphere, 850 ℃ of heat treatment 2h, obtain graphene nanometer sheet and WS
2composite nano materials, graphene nanometer sheet and WS in composite nano materials
2the ratio of amount be 2: 1.SEM, EDS, XRD and tem analysis show that composite material is graphene nanometer sheet and WS
2composite nano materials.
3) with the above-mentioned graphene nanometer sheet making and WS
2composite nano materials as electroactive substance, prepare electrode, nano composite material active material and acetylene black are under agitation fully mixed with the 1-METHYLPYRROLIDONE solution of the Kynoar of mass concentration 5%, the uniform pastel of furnishing, this pastel is coated onto equably on the Copper Foil of collector, then vacuumize 12h at 120 ℃, obtains electrode through roll extrusion after taking-up again.Wherein the mass percentage content of each component is: nano composite material active material 80%, acetylene black 10%, Kynoar 10%.
By the method for embodiment 1, be assembled into test battery and carry out the test of the chemical property of electrode.
As a comparison, the Cys of 7.5mmol is dissolved in 63ml deionized water, then add by the prepared graphite oxide nanometer sheet of the graphite of 2.5mmol (0.03g) and add in this solution, ultrasonic processing 1.5h, graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, then this mixture is transferred in hydrothermal reaction kettle, at 270 ℃, hydro-thermal reaction is 28 hours, naturally cooling, centrifugation, with deionized water, fully wash rear collection dry, the product obtaining is graphene nanometer sheet.With resulting graphene nanometer sheet, as electroactive substance, by above-mentioned same method preparation work electrode, and test its electrochemistry doff lithium reversible capacity and cycle performance by above-mentioned same method.
Electrochemical results shows: with synthetic graphene nanometer sheet and the WS of embodiment 2
2the electrode prepared of composite nano materials, its initial reversible capacity reaches 1030mAh/g, after circulation 100 times, capacity is 995 mAh/g.And take the electrode that the graphene nanometer sheet of Hydrothermal Synthesis is active material, its initial reversible capacity is 753mAh/g, but after circulation 100 times, its capacity loss are to 452mAh/g.Illustrate with graphene nanometer sheet and WS
2the electrode prepared of composite nano materials than graphene nano plate electrode, there is the stable circulation performance of higher specific capacity and Geng Gao.
Embodiment 3:
1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, 5.0mmol (0.06g) graphite powder is distributed in the 25mL concentrated sulfuric acid, adds KMnO under stirring
4, institute adds KMnO
4quality be 4 times of graphite, stir 50 minutes, temperature rises to 35 ℃ of left and right, adds 50ml deionized water, stirs 30 minutes, adds the H of 20ml mass concentration 30%
2o
2, stir 15 minutes, through centrifugation, with obtaining graphite oxide nanometer sheet after mass concentration 5%HCl solution, deionized water and acetone cyclic washing;
2) 1.25mmol wolframic acid is dissolved in 63ml deionized water, form the solution of 0.02M, add the Cys of 15mmol to stir, Cys is 12: 1 with the ratio of the amount of wolframic acid, then by the 1st) the prepared graphite oxide nanometer sheet of graphite of 5.0mmol for step (0.06g) adds in this solution, in the amount of substance of graphite raw material used and solution, wolframic acid amount ratio is 4: 1, ultrasonic processing 2.0h, graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, then this mixture is transferred in hydrothermal reaction kettle, at 250 ℃, hydro-thermal reaction is 30 hours, naturally cooling, centrifugation, with deionized water, fully wash rear collection dry, finally at 90%N
2-10%H
2in atmosphere, 800 ℃ of heat treatment 2h, obtain graphene nanometer sheet and WS
2composite nano materials, graphene nanometer sheet and WS in composite nano materials
2the ratio of amount be 4: 1.SEM, EDS and XRD analysis show that composite material is graphene nanometer sheet and WS
2composite nano materials.
3) with the above-mentioned graphene nanometer sheet making and WS
2composite nano materials as electroactive substance, prepare electrode, nano composite material active material and acetylene black are under agitation fully mixed with the 1-METHYLPYRROLIDONE solution of the Kynoar of mass concentration 5%, the uniform pastel of furnishing, this pastel is coated onto equably on the Copper Foil of collector, then vacuumize 12h at 120 ℃, obtains electrode through roll extrusion after taking-up again.Wherein the mass percentage content of each component is: nano composite material active material 80%, acetylene black 10%, Kynoar 10%.
By the method for embodiment 1, be assembled into test battery and carry out the test of the chemical property of electrode.
Electrochemical results shows: with synthetic graphene nanometer sheet and the WS of embodiment 3
2the electrode prepared of composite nano materials, its initial reversible capacity reaches 890mAh/g, after circulation 100 times, capacity is 858mAh/g.Illustrate with graphene nanometer sheet and WS
2the electrode prepared of composite nano materials than the WS of above-mentioned position comparison
2nano material electrode and graphene nano plate electrode have higher specific capacity and better stable circulation performance.
Embodiment 4:
1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, 4.5mmol (0.054g) graphite powder is distributed in the 25mL concentrated sulfuric acid, adds KMnO under stirring
4, institute adds KMnO
4quality be 3 times of graphite, stir 40 minutes, temperature rises to 30 ℃ of left and right, adds 50ml deionized water, stirs 24 minutes, adds the H of 20ml mass concentration 30%
2o
2, stir 10 minutes, through centrifugation, with obtaining graphite oxide nanometer sheet after mass concentration 5%HCl solution, deionized water and acetone cyclic washing;
2) 1.5mmol wolframic acid is dissolved in 60ml deionized water, form the solution of 0.03M, add the Cys of 15mmol to stir, Cys is 10: 1 with the ratio of the amount of wolframic acid, after fully stirring, then by the 1st) the prepared graphite oxide nanometer sheet of graphite of 4.5mmol for step (0.054g) adds in this solution, in the amount of substance of graphite raw material used and solution, wolframic acid amount ratio is 3: 1, ultrasonic processing 1.5h, graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, then this mixture is transferred in hydrothermal reaction kettle, at 280 ℃, hydro-thermal reaction is 26 hours, naturally cooling, centrifugation, with deionized water, fully wash rear collection dry, finally at 90%N
2-10%H
2in atmosphere, 900 ℃ of heat treatment 2h, obtain graphene nanometer sheet and WS
2composite nano materials, graphene nanometer sheet and WS in composite nano materials
2the ratio of amount be 3: 1.SEM, EDS, XRD analysis shows that composite material is graphene nanometer sheet and WS
2composite nano materials;
3) with the above-mentioned graphene nanometer sheet making and WS
2composite nano materials as electroactive substance, prepare electrode, nano composite material active material and acetylene black are under agitation fully mixed with the 1-METHYLPYRROLIDONE solution of the Kynoar of mass concentration 5%, the uniform pastel of furnishing, this pastel is coated onto equably on the Copper Foil of collector, then vacuumize 12h at 120 ℃, obtains electrode through roll extrusion after taking-up again.Wherein the mass percentage content of each component is: nano composite material active material 85%, acetylene black 5%, Kynoar 10%.
By the method for embodiment 1, be assembled into test battery and carry out the test of the chemical property of electrode.Test result shows: with synthetic graphene nanometer sheet and the WS of embodiment 4
2the electrode prepared of composite nano materials, its initial reversible capacity is 806mAh/g, after circulation 100 times, capacity is 782mAh/g.Illustrate with graphene nanometer sheet and WS
2the electrode prepared of composite nano materials than the WS of above-mentioned comparative example
2nano material electrode and graphene nano plate electrode have higher specific capacity and better stable circulation performance.
Embodiment 5:
1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, 4.2mmol (0.051g) graphite powder is distributed in the 25mL concentrated sulfuric acid, adds KMnO under stirring
4, institute adds KMnO
4quality be 4 times of graphite, stir 52 minutes, temperature rises to 32 ℃ of left and right, adds 40ml deionized water, stirs 15 minutes, adds the H of 15ml mass concentration 30%
2o
2, stir 8 minutes, through centrifugation, with obtaining graphite oxide nanometer sheet after mass concentration 5%HCl solution, deionized water and acetone cyclic washing;
2) 4.2mmol wolframic acid is dissolved in 60ml deionized water, form the solution of 0.07M, add the Cys of 25.2mmol to stir, Cys is 6: 1 with the ratio of the amount of wolframic acid, then by the 1st) the prepared graphite oxide nanometer sheet of graphite of 4.2mmol for step (0.051g) adds in this solution, in the amount of substance of graphite raw material used and solution, wolframic acid amount ratio is 1: 1, ultrasonic processing 1.5h, graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, then this mixture is transferred in hydrothermal reaction kettle, at 280 ℃, hydro-thermal reaction is 25 hours, naturally cooling, centrifugation, with deionized water, fully wash rear collection dry, finally at 90%N
2-10%H
2in atmosphere, 950 ℃ of heat treatment 2h, obtain graphene nanometer sheet and WS
2composite nano materials, graphene nanometer sheet and WS in composite nano materials
2the ratio of the amount of nano material is 1: 1.SEM, EDS, XRD analysis shows that composite material is graphene nanometer sheet and WS
2composite nano materials;
3) with the above-mentioned graphene nanometer sheet making and WS
2composite nano materials as electroactive substance, prepare electrode, nano composite material active material and acetylene black are under agitation fully mixed with the 1-METHYLPYRROLIDONE solution of the Kynoar of mass concentration 5%, the uniform pastel of furnishing, this pastel is coated onto equably on the Copper Foil of collector, then vacuumize 12h at 120 ℃, obtains electrode through roll extrusion after taking-up again.Wherein the mass percentage content of each component is: nano composite material active material 80%, acetylene black 10%, Kynoar 10%.
By the method for embodiment 1, be assembled into test battery and carry out the test of the chemical property of electrode.
Electrochemical results shows: with synthetic graphene nanometer sheet and the WS of embodiment 5
2the electrode prepared of composite nano materials, its initial reversible capacity is 756mAh/g, after circulation 100 times, capacity is 732mAh/g.Illustrate with graphene nanometer sheet and WS
2the electrode prepared of composite nano materials than the WS of above-mentioned comparative example
2nano material electrode and graphene nano plate electrode have higher specific capacity and better stable circulation performance.
Claims (1)
1. a silicon/carbon/graphite in lithium ion batteries alkene/WS
2composite nano materials electrode, the active material that it is characterized in that this electrode is graphene nanometer sheet and WS
2composite nano materials, all the other are acetylene black and Kynoar, the mass percentage content of each component is: composite nano materials active material 80-85%, acetylene black 5-10%, Kynoar 10%, wherein, graphene nanometer sheet and WS in composite nano materials active material
2the amount ratio of nano material is 1: 1～4: 1;
Silicon/carbon/graphite in lithium ion batteries alkene/WS
2the preparation method of composite nano materials electrode comprises the following steps:
1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, 0.015-0.072g graphite powder is distributed in the 20-25mL concentrated sulfuric acid, adds KMnO under stirring
4, institute adds KMnO
4quality be graphite powder 3-4 doubly, stir 30-60 minute, temperature rises to 30-35 ℃, adds 40-50ml deionized water, stirs 20-30 minute, adds the H of 10-15ml mass concentration 30%
2o
2, stir 5-20 minute, through centrifugation, with obtaining graphite oxide nanometer sheet after mass concentration 5%HCl solution, deionized water and acetone cyclic washing;
2) wolframic acid is dissolved in to the solution that forms 0.02～0.07M in deionized water, add Cys as sulphur source and reducing agent, Cys is 5: 1～12: 1 with the amount ratio of wolframic acid, again will be by the 1st) the preparation-obtained graphite oxide nanometer sheet of step adds in this solution, the 1st) amount of step graphite powder raw material used is 1: 1～4: 1 with the amount ratio of wolframic acid, ultrasonic processing 1-2h, graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, mixture obtained above is proceeded in the hydrothermal reaction kettle of inner liner polytetrafluoroethylene and seal, at 250-290 ℃ of reaction 20-36h, the product obtaining is through centrifugation, and with deionized water and absolute ethanol washing, dry, finally at 90%N
2-10%H
2in atmosphere, 800-1000 ℃ of heat treatment 2h, obtains graphene nanometer sheet and WS
2composite nano materials,
3) by graphene nanometer sheet/WS
2composite nano materials is as the active material of electrode, under agitation fully mix the uniform pastel of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black and mass concentration 5%, each constituent mass percentage is: composite nano materials active material 80-85%, acetylene black 5-10%, Kynoar 10%, this pastel is coated onto equably on the Copper Foil of collector, and dry, roll extrusion obtains electrode.
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