CN102214816A - 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
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 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 78
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 66
- 239000010439 graphite Substances 0.000 claims abstract description 66
- 239000011149 active material Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 26
- 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 70
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 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 28
- 238000002360 preparation method Methods 0.000 claims description 28
- 239000004201 L-cysteine Substances 0.000 claims description 23
- 235000013878 L-cysteine Nutrition 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 21
- 238000005119 centrifugation Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 11
- 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
- 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
- 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
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [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
- 239000000126 substance Substances 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 22
- 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
- 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
- 239000010410 layer Substances 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
- 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000005516 engineering process 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
- 230000000694 effects 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
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 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
- 230000000536 complexating effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 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
- 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
2Composite material belongs to mechanism of new electrochemical power sources and new energy materials field as the high power capacity of electroactive substance preparation and the lithium ion cell electrode of stable cycle performance.
Background technology
Lithium ion battery has excellent properties such as specific energy height, memory-less effect, environmental friendliness, has been widely used in portable movable electrical appliances such as mobile phone and notebook computer.As electrokinetic cell, lithium ion battery also is 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 microballoon, natural modified graphite and Delanium etc.) at present, and these graphite materials have stable circulation performance preferably, but its capacity is lower, and the theoretical capacity of graphite is 372mAh/g.A new generation's lithium ion battery is had higher requirement to the capacity and the stable circulation performance of electrode material, 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, has important scientific research meaning and application prospects.The finder of grapheme material obtains the Nobel Prize in 2010 and has excited the very big interest of people to grapheme material research especially.Recently, graphene nanometer sheet and composite material thereof synthetic and obtained extensive concern as the research of lithium ion battery negative material.Theoretical Calculation shows that the both sides of graphene nanometer sheet can store lithium, 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 of compound composite material storage lithium capacity is respectively 730 and 784mAh/g.But the cycle performance of some bibliographical information Graphenes and composite electrode thereof is still waiting to improve, and cycle performance is not good enough to be likely because the unstable or reunion of graphene nano chip architecture in inappropriate arrangement of graphene nanometer sheet and the charge and discharge process.
On the other hand, WS
2Typical 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 then is more weak Van der Waals force, peels off easily between layer and the layer.WS
2More weak interlaminar action power and bigger interlamellar spacing allow to be reflected at its interlayer by insertion and introduce external atom or molecule.Such characteristic makes WS
2Material can be used as the material of main part that inserts reaction.Therefore, WS
2Be a kind of rising electrochemical lithium storage that is used for heavy-duty battery and the electrode material of 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 the tungsten oxide nanometer rod
2Nanometer sheet, its electrochemistry storage lithium capacity is 377mAh/g, but 30 later its capability retentions that circulate have only kept 64% of initial capacity, and its capacity and cycle performance all remain further to be improved.In addition, though 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 relatively poor.
Because graphene nanometer sheet and WS
2Nano material all has good electrochemistry storage lithium performance, have good application prospects as the lithium ion battery negative material of a new generation, but their electrochemistry storage lithium capacity and stable circulation performance is still waiting further raising.If with 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, helps the electron transport in the electrochemical electrode course of reaction, the chemical property of reinforced composite; The superpower mechanical property performance of Graphene helps keeping the stable of electrode structure in the charge and discharge process, and composite material also can suppress the reunion of graphene nanometer sheet, therefore improves its stable circulation performance greatly.Graphene nanometer sheet and WS in addition
2Nano material is compound, the big ∏ key and the WS of graphene nanometer sheet
2The interaction of surface 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, less than WS
2Interlamellar spacing, the electrochemistry of the suitable favourable reinforced composite of interlamellar spacing structure storage lithium performance.
But, up to the present, with graphene nanometer sheet/WS
2Nano composite material prepares the lithium ion cell electrode with high power capacity and high stable circulation performance as electroactive substance and yet there are no open report.
The application of biological micromolecule in nano material is synthetic recently obtained people's extensive concern.The L-cysteine 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.The L-cysteine 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] synthesized the Bi of floriform appearance with the L-cysteine
2S
3Nano structural material.But up to the present, use the L-cysteine and assist synthesizing graphite alkene and WS
2Composite nano materials and 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 the 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
2The composite nano materials electrode is characterized in that the preparation method may further comprise the steps:
1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, the 0.015-0.072g graphite powder is distributed in the 20-25mL concentrated sulfuric acid, stirs adding KMnO down
4, institute adds KMnO
4Quality be graphite 3-4 doubly, stirred 30-60 minute, temperature rises to about 30-35 ℃, adds the 40-50ml deionized water, stirs the H of adding 10-15ml mass concentration 30% 20-30 minute
2O
2, stirred 5-20 minute, through centrifugation, with obtaining the graphite oxide nanometer sheet behind mass concentration 5%HCl solution, deionized water and the acetone cyclic washing;
2) wolframic acid is dissolved in the solution that forms 0.02～0.07M in the deionized water, adding the L-cysteine is sulphur source and reducing agent, the L-cysteine is 5: 1～12: 1 with the ratio of the amount of wolframic acid, again will be by the 1st) preparation-obtained graphite oxide nanometer sheet of step adds in this solution, the 1st) used graphite raw material amount of substance of step is 1: 1～4: 1 with the ratio of the amount of wolframic acid, sonicated 1-2h, the graphite oxide nanometer sheet is well dispersed in the hydro-thermal reaction solution, this mixture changed over to hydrothermal reaction kettle seal, at 250-290 ℃ of reaction 20-36h, the product centrifugation that obtains, and with deionized water and absolute ethanol washing, drying is at last at 90%N
2-10%H
2800-1000 ℃ of heat treatment 2h obtains graphene nanometer sheet and WS in the atmosphere
2Composite nano materials.
3) with 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 N-methyl pyrrolidone 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 on the Copper Foil as collector equably, drying, roll extrusion obtains electrode.
Method of the present invention has the gentle and technology characteristic of simple of reaction condition.The inventive method graphene nanometer sheet and WS
2Composite nano materials be that the electrode of lithium ion battery of the active material preparation of electrode has high electrochemistry storage lithium capacity and overstable cycle performance.
Method of the present invention compared with the prior art has following outstanding advantage:
(1) because graphene nanometer sheet has excellent properties such as high specific area, superpower mechanical property, high conduction and heat conduction, therefore, the present invention is with graphene nanometer sheet and WS
2Composite nano materials prepare electrode and help electron transport in the electrode process, strengthen the chemical property of composite nano materials electrode.In addition, because the big ∏ key and the WS of graphene nanometer sheet
2The interaction of surface electronic structure, graphene nanometer sheet and WS
2Nano material compound can form the electronic structure between a kind of new different material, and the electronics of participation effect can the height delocalization, helps the quick transmission of electronics in the electrochemical reaction process.This graphene nanometer sheet and WS
2Composite nano materials can significantly strengthen its chemical property as electrode material electrochemistry storage lithium.
(2) in the course of reaction of the present invention, stannic oxide/graphene nano sheet in-situ reducing becomes graphene nanometer sheet, and is compounded to form composite material with Wolfram disulfide nano material that the original position hydro-thermal reaction forms.Its advantage is: the graphite oxide nanometer sheet contains abundant oxygen-containing functional group (as: hydroxyl, carbonyl and carboxyl etc.), in hydro-thermal reaction solution, reunited again no longer easily later on or be deposited in together by ultrasonic dispersion, and the functional group on graphite oxide surface can be adsorbed on tungstate radicle the surface of graphite oxide nanometer sheet by complexing, can be that generated in-situ graphene nanometer sheet and Wolfram disulfide nano material height are evenly compound in the reproducibility hydrothermal reaction process, heat treatment obtains the composite nano materials of graphene nanometer sheet and tungsten disulfide.
(3) the L-cysteine 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, the L-cysteine can form coordination with the center tungsten ion in the tungstate radicle in the solution.Simultaneously because the existence of stannic oxide/graphene nano sheet in the solution, just formed the coordination mode of stannic oxide/graphene nano sheet-tungstate radicle-L-cysteine, can be evenly compound nano material of generated in-situ graphene nanometer sheet and Wolfram disulfide nano material height in the reproducibility hydrothermal reaction process, 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 the preparation process, can suppress the excessive crystal growth and the reunion of tungsten disulfide in the heat treatment process, obtain relative crystallinity is low and the number of plies is less the Wolfram disulfide nano material 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 the reaction condition gentleness, and technology is simple, the advantage of productive rate height and favorable reproducibility.Because graphene nanometer sheet and WS
2Synergy, the present invention is with graphene nanometer sheet and WS
2Composite nano materials be that the electrode of lithium ion battery of the active material preparation of electrode has 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, stirs adding 0.03g KMnO down
4, institute adds KMnO
4Quality be 3 times of graphite, stirred 30 minutes, temperature rises to about 30 ℃, adds the 45ml deionized water, stirs the H of adding 10ml mass concentration 30% 20 minutes
2O
2, stirred 5 minutes, through centrifugation, with obtaining the graphite oxide nanometer sheet behind mass concentration 5%HCl solution, deionized water and the acetone cyclic washing;
2) the 1.25mmol wolframic acid is dissolved in the 63ml deionized water, form the solution of 0.02M, the L-cysteine that adds 6.25mmol stirs, the L-cysteine is 5.0: 1 with the ratio of the amount of wolframic acid, then with the 1st) step add in this solution with the prepared graphite oxide nanometer sheet of the graphite of 1.25mmol (0.015g), wolframic acid amount ratio is 1: 1 in the amount of substance of used graphite raw material and the solution, sonicated 1.0h, the graphite oxide nanometer sheet is well dispersed in the hydro-thermal reaction solution, then this mixture is transferred in the hydrothermal reaction kettle, in 26 ℃ of following hydro-thermal reactions 24 hours, natural cooling, centrifugation is fully washed the back with deionized water and is collected also drying, at last at 90%N
2-10%H
2800 ℃ of heat treatment 2h obtain graphene nanometer sheet and WS in the atmosphere
2Composite nano materials, graphene nanometer sheet and WS in the 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 above-mentioned graphene nanometer sheet that makes and WS
2Composite nano materials prepare electrode as electroactive substance, nano composite material active material and acetylene black are under agitation fully mixed with the N-methyl pyrrolidone solution of the Kynoar of mass concentration 5%, the uniform pastel of furnishing, this pastel is coated onto on the Copper Foil as collector equably, at 120 ℃ of following vacuumize 12h, obtain electrode through roll extrusion again after the taking-up then.Wherein the mass percentage content of each component is: nano composite material active material 80%, acetylene black 10%, Kynoar 10%.
4) use the conduct of lithium paper tinsel 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.Charging and discharging currents density 100mA/g, voltage range 0.01～3.00V are carried out in the test of battery constant current charge-discharge on programme controlled auto charge and discharge instrument.
As a comparison, the 1.25mmol wolframic acid is dissolved in the 63ml deionized water, form the solution of 0.02M, the L-cysteine that adds 6.25mmol stirs, and the L-cysteine is 5.0: 1 with the ratio of the amount of wolframic acid, this solution is transferred in the hydrothermal reaction kettle, in 260 ℃ of following hydro-thermal reactions 24 hours, natural cooling, centrifugation, fully wash the back with deionized water and collect also drying, at last at 90%N
2-10%H
2800 ℃ of heat treatment 2h obtain WS in the atmosphere
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: the graphene nanometer sheet and the WS that use embodiment 1 to synthesize
2The electrode of composite nano materials preparation, its initial reversible capacity reaches 743mAh/g, after circulation 100 times, capacity is 731mAh/g.And with the synthetic WS of hydro-thermal
2Nano material be the electrode of active material, its initial reversible capacity is up to 567mAh/g, but the circulation 100 times after its capacity drop to 322mAh/g.Illustrate with graphene nanometer sheet and WS
2The electrode of composite nano materials preparation compare WS
2The nano 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, stirs adding KMnO down
4, institute adds KMnO
4Quality be 4 times of graphite, stirred 40 minutes, temperature rises to about 33 ℃, adds the 50ml deionized water, stirs the H of adding 12ml mass concentration 30% 25 minutes
2O
2, stirred 5-10 minute, through centrifugation, with obtaining the graphite oxide nanometer sheet behind mass concentration 5%HCl solution, deionized water and the acetone cyclic washing;
2) the 1.25mmol wolframic acid is dissolved in the 63ml deionized water, form the solution of 0.02M, the L-cysteine that adds 7.5mmol stirs, wherein the L-cysteine is 6: 1 with the ratio of the amount of wolframic acid, then with the 1st) step add in this solution with the prepared graphite oxide nanometer sheet of the graphite of 2.5mmol (0.03g), wolframic acid amount ratio is 2: 1 in the amount of substance of used graphite raw material and the solution, sonicated 1.5h, the graphite oxide nanometer sheet is well dispersed in the hydro-thermal reaction solution, then this mixture is transferred in the hydrothermal reaction kettle, in 270 ℃ of following hydro-thermal reactions 28 hours, natural cooling, centrifugation is fully washed the back with deionized water and is collected also drying, at last at 90%N
2-10%H
2850 ℃ of heat treatment 2h obtain graphene nanometer sheet and WS in the atmosphere
2Composite nano materials, graphene nanometer sheet and WS in the 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 above-mentioned graphene nanometer sheet that makes and WS
2Composite nano materials prepare electrode as electroactive substance, nano composite material active material and acetylene black are under agitation fully mixed with the N-methyl pyrrolidone solution of the Kynoar of mass concentration 5%, the uniform pastel of furnishing, this pastel is coated onto on the Copper Foil as collector equably, at 120 ℃ of following vacuumize 12h, obtain electrode through roll extrusion again after the taking-up then.Wherein the mass percentage content of each component is: nano composite material active material 80%, acetylene black 10%, Kynoar 10%.
Method by embodiment 1 is assembled into test battery and carries out the test of the chemical property of electrode.
As a comparison, the L-cysteine of 7.5mmol is dissolved in the 63ml deionized water, add then and add in this solution with the prepared graphite oxide nanometer sheet of the graphite of 2.5mmol (0.03g), sonicated 1.5h, the graphite oxide nanometer sheet is well dispersed in the hydro-thermal reaction solution, then this mixture is transferred in the hydrothermal reaction kettle, in 270 ℃ of following hydro-thermal reactions 28 hours, natural cooling, centrifugation, fully wash the back with deionized water and collect also drying, the product that obtains is a graphene nanometer sheet.As electroactive substance,, and test its electrochemistry doff lithium reversible capacity and cycle performance with resultant graphene nanometer sheet by above-mentioned same method by above-mentioned same method preparation work electrode.
Electrochemical results shows: the graphene nanometer sheet and the WS that use embodiment 2 to synthesize
2The electrode of composite nano materials preparation, its initial reversible capacity reaches 1030mAh/g, after circulation 100 times, capacity is 995 mAh/g.And the graphene nanometer sheet that synthesizes with hydro-thermal is the electrode of active material, and its initial reversible capacity is 753mAh/g, but drops to 452mAh/g at 100 later its capacity of circulation.Illustrate with graphene nanometer sheet and WS
2The electrode of composite nano materials preparation have the stable circulation performance of higher specific capacity and Geng Gao than graphene nano plate electrode.
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, stirs adding KMnO down
4, institute adds KMnO
4Quality be 4 times of graphite, stirred 50 minutes, temperature rises to about 35 ℃, adds the 50ml deionized water, stirs the H of adding 20ml mass concentration 30% 30 minutes
2O
2, stirred 15 minutes, through centrifugation, with obtaining the graphite oxide nanometer sheet behind mass concentration 5%HCl solution, deionized water and the acetone cyclic washing;
2) the 1.25mmol wolframic acid is dissolved in the 63ml deionized water, form the solution of 0.02M, the L-cysteine that adds 15mmol stirs, the L-cysteine is 12: 1 with the ratio of the amount of wolframic acid, then with the 1st) step add in this solution with the prepared graphite oxide nanometer sheet of the graphite of 5.0mmol (0.06g), wolframic acid amount ratio is 4: 1 in the amount of substance of used graphite raw material and the solution, sonicated 2.0h, the graphite oxide nanometer sheet is well dispersed in the hydro-thermal reaction solution, then this mixture is transferred in the hydrothermal reaction kettle, in 250 ℃ of following hydro-thermal reactions 30 hours, natural cooling, centrifugation is fully washed the back with deionized water and is collected also drying, at last at 90%N
2-10%H
2800 ℃ of heat treatment 2h obtain graphene nanometer sheet and WS in the atmosphere
2Composite nano materials, graphene nanometer sheet and WS in the 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 above-mentioned graphene nanometer sheet that makes and WS
2Composite nano materials prepare electrode as electroactive substance, nano composite material active material and acetylene black are under agitation fully mixed with the N-methyl pyrrolidone solution of the Kynoar of mass concentration 5%, the uniform pastel of furnishing, this pastel is coated onto on the Copper Foil as collector equably, at 120 ℃ of following vacuumize 12h, obtain electrode through roll extrusion again after the taking-up then.Wherein the mass percentage content of each component is: nano composite material active material 80%, acetylene black 10%, Kynoar 10%.
Method by embodiment 1 is assembled into test battery and carries out the test of the chemical property of electrode.
Electrochemical results shows: the graphene nanometer sheet and the WS that use embodiment 3 to synthesize
2The electrode of composite nano materials preparation, its initial reversible capacity reaches 890mAh/g, after circulation 100 times, capacity is 858mAh/g.Illustrate with graphene nanometer sheet and WS
2The electrode of composite nano materials preparation than above-mentioned position WS relatively
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, stirs adding KMnO down
4, institute adds KMnO
4Quality be 3 times of graphite, stirred 40 minutes, temperature rises to about 30 ℃, adds the 50ml deionized water, stirs the H of adding 20ml mass concentration 30% 24 minutes
2O
2, stirred 10 minutes, through centrifugation, with obtaining the graphite oxide nanometer sheet behind mass concentration 5%HCl solution, deionized water and the acetone cyclic washing;
2) the 1.5mmol wolframic acid is dissolved in the 60ml deionized water, form the solution of 0.03M, the L-cysteine that adds 15mmol stirs, the L-cysteine is 10: 1 with the ratio of the amount of wolframic acid, after fully stirring, then with the 1st) step add in this solution with the prepared graphite oxide nanometer sheet of the graphite of 4.5mmol (0.054g), wolframic acid amount ratio is 3: 1 in the amount of substance of used graphite raw material and the solution, sonicated 1.5h, the graphite oxide nanometer sheet is well dispersed in the hydro-thermal reaction solution, then this mixture is transferred in the hydrothermal reaction kettle, in 280 ℃ of following hydro-thermal reactions 26 hours, natural cooling, centrifugation, fully wash the back with deionized water and collect also drying, at last at 90%N
2-10%H
2900 ℃ of heat treatment 2h obtain graphene nanometer sheet and WS in the atmosphere
2Composite nano materials, graphene nanometer sheet and WS in the composite nano materials
2The ratio of amount be 3: 1.SEM, EDS, XRD analysis show that composite material is graphene nanometer sheet and WS
2Composite nano materials;
3) with above-mentioned graphene nanometer sheet that makes and WS
2Composite nano materials prepare electrode as electroactive substance, nano composite material active material and acetylene black are under agitation fully mixed with the N-methyl pyrrolidone solution of the Kynoar of mass concentration 5%, the uniform pastel of furnishing, this pastel is coated onto on the Copper Foil as collector equably, at 120 ℃ of following vacuumize 12h, obtain electrode through roll extrusion again after the taking-up then.Wherein the mass percentage content of each component is: nano composite material active material 85%, acetylene black 5%, Kynoar 10%.
Method by embodiment 1 is assembled into test battery and carries out the test of the chemical property of electrode.Test result shows: the graphene nanometer sheet and the WS that use embodiment 4 to synthesize
2The electrode of composite nano materials preparation, its initial reversible capacity is 806mAh/g, after circulation 100 times, capacity is 782mAh/g.Illustrate with graphene nanometer sheet and WS
2The electrode of composite nano materials preparation 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, stirs adding KMnO down
4, institute adds KMnO
4Quality be 4 times of graphite, stirred 52 minutes, temperature rises to about 32 ℃, adds the 40ml deionized water, stirs the H of adding 15ml mass concentration 30% 15 minutes
2O
2, stirred 8 minutes, through centrifugation, with obtaining the graphite oxide nanometer sheet behind mass concentration 5%HCl solution, deionized water and the acetone cyclic washing;
2) the 4.2mmol wolframic acid is dissolved in the 60ml deionized water, form the solution of 0.07M, the L-cysteine that adds 25.2mmol stirs, the L-cysteine is 6: 1 with the ratio of the amount of wolframic acid, then with the 1st) step add in this solution with the prepared graphite oxide nanometer sheet of the graphite of 4.2mmol (0.051g), wolframic acid amount ratio is 1: 1 in the amount of substance of used graphite raw material and the solution, sonicated 1.5h, the graphite oxide nanometer sheet is well dispersed in the hydro-thermal reaction solution, then this mixture is transferred in the hydrothermal reaction kettle, in 280 ℃ of following hydro-thermal reactions 25 hours, natural cooling, centrifugation is fully washed the back with deionized water and is collected also drying, at last at 90%N
2-10%H
2950 ℃ of heat treatment 2h obtain graphene nanometer sheet and WS in the atmosphere
2Composite nano materials, graphene nanometer sheet and WS in the composite nano materials
2The ratio of the amount of nano material is 1: 1.SEM, EDS, XRD analysis show that composite material is graphene nanometer sheet and WS
2Composite nano materials;
3) with above-mentioned graphene nanometer sheet that makes and WS
2Composite nano materials prepare electrode as electroactive substance, nano composite material active material and acetylene black are under agitation fully mixed with the N-methyl pyrrolidone solution of the Kynoar of mass concentration 5%, the uniform pastel of furnishing, this pastel is coated onto on the Copper Foil as collector equably, at 120 ℃ of following vacuumize 12h, obtain electrode through roll extrusion again after the taking-up then.Wherein the mass percentage content of each component is: nano composite material active material 80%, acetylene black 10%, Kynoar 10%.
Method by embodiment 1 is assembled into test battery and carries out the test of the chemical property of electrode.
Electrochemical results shows: the graphene nanometer sheet and the WS that use embodiment 5 to synthesize
2The electrode of composite nano materials preparation, its initial reversible capacity is 756mAh/g, after circulation 100 times, capacity is 732mAh/g.Illustrate with graphene nanometer sheet and WS
2The electrode of composite nano materials preparation 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 (2)
1. silicon/carbon/graphite in lithium ion batteries alkene/WS
2The composite 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 75-85%, acetylene black 5-10%, Kynoar 10%, wherein, graphene nanometer sheet and WS in the composite nano materials active material
2The ratio of the amount of nano material is 1: 1～4: 1.
2. the described a kind of silicon/carbon/graphite in lithium ion batteries alkene/WS of claim 1
2The composite nano materials electrode is characterized in that the preparation method may further comprise the steps:
1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, the 0.015-0.072g graphite powder is distributed in the 20-25mL concentrated sulfuric acid, stirs adding KMnO down
4, institute adds KMnO
4Quality be graphite 3-4 doubly, stirred 30-60 minute, temperature rises to about 30-35 ℃, adds the 40-50ml deionized water, stirs the H of adding 10-15ml mass concentration 30% 20-30 minute
2O
2, stirred 5-20 minute, through centrifugation, with obtaining the graphite oxide nanometer sheet behind mass concentration 5%HCl solution, deionized water and the acetone cyclic washing;
2) wolframic acid is dissolved in the solution that forms 0.02～0.07M in the deionized water, adding the L-cysteine is sulphur source and reducing agent, the L-cysteine is 5: 1～12: 1 with the ratio of the amount of wolframic acid, again will be by the 1st) preparation-obtained graphite oxide nanometer sheet of step adds in this solution, the 1st) amount of used graphite powder raw material of step is 1: 1～4: 1 with the ratio of the amount of wolframic acid, sonicated 1-2h, the graphite oxide nanometer sheet is well dispersed in the hydro-thermal reaction solution, this mixture is changed in the hydrothermal reaction kettle of inner liner polytetrafluoroethylene and seal, at 250-290 ℃ of reaction 20-36h, the product centrifugation that obtains, and with deionized water and absolute ethanol washing, drying is at last at 90%N
2-10%H
2800-1000 ℃ of heat treatment 2h obtains graphene nanometer sheet and WS in the atmosphere
2Composite nano materials;
3) with 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 N-methyl pyrrolidone 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 on the Copper Foil as collector equably, drying, roll extrusion obtains electrode.
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Address after: 313100 2-3 floor of No. 2 workshop, No. 559 the Great Wall Road, Changxing County Taihu street, Huzhou, Zhejiang. Patentee after: Zhejiang Tianhong lithium battery Limited by Share Ltd. Address before: 313000 Changxin economic and Technological Development Zone, Huzhou, Zhejiang Patentee before: CHANGXING TIANHONG LITHIUM-ION BATTERY TECHNOLOGY Co.,Ltd. |
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