CN102142541B - High capacity and stable cyclic performance lithium ion battery electrode and preparation method thereof - Google Patents
High capacity and stable cyclic performance lithium ion battery electrode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high capacity and stable cyclic performance lithium ion battery electrode and a preparation method thereof. The invention is characterized in that: the electrode comprises the following components in percentage by mass: 75 to 85 percent of graphene nano slice/molybdenum disulfide (MoS2) compound nano material serving as an active substance, and 5 to 10 percent of acetylene black and 5 to 15 percent of polyvinylidene fluoride; and the mass ratio of the graphene nano slice to the MoS2 compound nano material in the compound nano material active substance is (1 to 1)-(4 to 1). The preparation method for the electrode comprises the following steps of: preparing an oxidized graphite nano slice by using graphite as a raw material by a chemical oxidization method; synthesizing by a one-step hydrothermal in-situ reduction method in the presence of the oxidized graphite nano slice to obtain a graphene nano slice/MoS2 compound nano material; and finally, preparing the electrode by using the graphene nano slice/MoS2 compound nano material as the active substance. The electrode has high electrochemical lithium storage reversible capacity and cyclic stabilization performance, and can be widely applied to new generation lithium ion batteries.
Description
Technical field
The present invention relates to lithium ion cell electrode and preparation method thereof, especially use graphene nanometer sheet/MoS
2the electrode of the lithium ion battery with high power capacity and stable cycle performance that composite nano materials is prepared as electroactive substance, belongs to the field of mechanism of new electrochemical power sources and new energy materials.
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).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 electrode production process and in charge and discharge process or to reunite.
On the other hand, MoS
2having typical sandwich layer structure, is covalent bonds in the layer of S-Mo-S, with weak Van der Waals force, mutually combines between layers, and its interlamellar spacing is 0.62nm.MoS
2industrial catalyst and the kollag under vacuum and hot conditions as hydro-desulfurization are widely studied and applied.MoS
2weak interlaminar action power and larger interlamellar spacing allow to react at its interlayer and introduce external atom or molecule by insertion.Such characteristic makes MoS
2material can be used as the material of main part that inserts reaction.Therefore, MoS
2electrode material [G.X.Wang, S.Bewlay, J.Yao, et al., Electrochem.Solid State, 2004, the 7:A321 of a kind of rising electrochemical lithium storage for heavy-duty battery and electrochemistry storage magnesium; X.L.Li, Y.D.Li, J.Phys.Chem.B, 2004,108:13893].
Nineteen ninety-five Miki etc. has studied amorphous MoS
2electrochemical lithiation and de-lithium performance (Y.Miki, D.Nakazato, H.Ikuta, et al., J.Power Sources, 1995,54:508), found that the amorphous MoS of their synthesized
2in powder, the reversible capacity of the electrochemistry doff lithium of the sample that performance is best only has 200mAh/g, and after circulation 100 times, its reversible capacity drops to 100mAh/g, is half of its initial capacity.Therefore, its reversible capacity and stable circulation performance also require further improvement.The electroactive material of synthesis of nano structure is an effective way improving its chemical property.Nearest Li etc. [J.Alloys Compounds, 2009,471 (1-2): 442-447] have synthesized the MoS of floriform appearance with the hydrothermal method that ionic liquid is assisted
2, its electrochemistry storage lithium reversible capacity reaches 850mAh/g, but their cycle performance of report is still not good enough, remains to be further improved.
In sum, graphene nanometer sheet and MoS
2nano material is all good electrochemistry storage lithium electrode material, 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 MoS
2the compound composite nano materials that obtains of composite nano materials, 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 MoS in addition
2compound, large ∏ key and the MoS 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 MoS
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/MoS
2electrochemistry embedding/lithium ionic insertion/deinsertion electrode that nano composite material is prepared the lithium ion battery with high power capacity and high stable circulation performance as electroactive substance yet there are no open report.
Summary of the invention
The object of the present invention is to provide lithium ion cell electrode and the preparation method of a kind of high power capacity and stable cycle performance.
The lithium ion cell electrode of a kind of high power capacity of the present invention and stable cycle performance, the active material that it is characterized in that this electrode is graphene nanometer sheet/MoS
2composite nano materials, all the other are acetylene black and Kynoar, the mass percentage content of each component is: nano composite material active material 75-85%, acetylene black 5-10%, Kynoar 5-15%, wherein, graphene nanometer sheet and MoS in nano composite material active material
2the ratio of the amount of composite nano materials is 1: 1～4: 1.
The preparation method of the lithium ion cell electrode of a kind of high power capacity of the present invention and stable cycle performance comprises the following steps:
1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, 0.015-0.12g 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 20-60 minute, temperature rises to 30-35 ℃ of left and right, adds 46ml deionized water, stirs 20-30 minute, adds the H of 10-15ml 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) molybdate is dissolved in to the solution that forms 0.02～0.05M in deionized water, add thioacetamide or thiocarbamide as sulphur source and reducing agent, thioacetamide or thiocarbamide are 5: 1～12: 1 with the ratio of the amount of molybdate, again by by the 1st) step adds in this solution by the graphite oxide nanometer sheet that the graphite raw material of X mol prepares, X is 1: 1～4: 1 with the ratio of the amount of molybdate, ultrasonic processing 1-2h, graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, this mixture is proceeded in the hydrothermal reaction kettle of inner liner polytetrafluoroethylene and seal, at 200-240 ℃ of reaction 24-36h, the product centrifugation obtaining, and with deionized water and absolute ethanol washing, dry, obtain graphene nanometer sheet/MoS
2composite nano materials.
3) by graphene nanometer sheet/MoS
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 5-15%, this pastel is coated onto equably on the Copper Foil of collector, vacuumize, roll extrusion obtains electrode.
Described molybdate is sodium molybdate or ammonium molybdate.
The present invention has following beneficial effect compared with the prior art:
1) due to graphene nanometer sheet and MoS
2there is typical sheet or layer structure, both good electrochemistry is store lithium electrode material, as lithium ion battery negative material of new generation, there is good application prospect, but their electrochemistry storage lithium capacity and stable circulation performance need further raising.If by graphene nanometer sheet and MoS
2the compound composite nano materials of preparing 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 MoS in addition
2compound, large ∏ key and the MoS 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 MoS
2interlamellar spacing, the electrochemistry storage lithium performance of the suitable favourable reinforced composite of interlamellar spacing structure.
2) the present invention prepares graphene nanometer sheet/MoS
2in the process of composite nano materials, by graphite oxide nanometer sheet in-situ reducing, become graphene nanometer sheet, and react the molybdenum disulfide nano Material cladding formation composite material forming with Situ Hydrothermal.Its advantage is: abundant oxygen-containing functional group (as: hydroxyl, carbonyl and carboxyl etc.) is contained on graphite oxide nanometer sheet surface, 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 molybdate on the surface of graphite oxide nanometer sheet by complexing, in reproducibility hydrothermal reaction process, can make better generated in-situ graphene nanometer sheet and molybdenum disulfide nano material height ground evenly compound.
3) the present invention is raw material with stannic oxide/graphene nano sheet and molybdate, thioacetamide or thiocarbamide, adopts Situ Hydrothermal reducing process one step to become out the nano composite material of graphene nanometer sheet/molybdenum bisuphide.Synthetic 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 MoS in composite Nano material
2mutual synergy between nano material, graphene nanometer sheet/MoS for the present invention
2composite nano materials is that electrode prepared by electroactive substance compares MoS
2nano material and graphene nano plate electrode have higher electrochemistry storage lithium reversible capacity and better stable circulation performance.In lithium ion battery of new generation, have a wide range of applications.
Accompanying drawing explanation
Fig. 1. graphene nanometer sheet/MoS that embodiment 1 is synthetic
2xRD figure and the SEM pattern of composite nano materials, graphene nanometer sheet and MoS in composite material
2the ratio of amount be 1: 1.
Fig. 2. graphene nanometer sheet/MoS of embodiment 1
2the MoS of composite nano materials electrode and Hydrothermal Synthesis
2electrochemistry storage lithium capacity and the cycle performance of nano material electrode.
(a) graphene nanometer sheet/MoS
2composite nano materials electrode, graphene nanometer sheet and MoS in composite material
2the ratio of amount be 1: 1;
(b) MoS of Hydrothermal Synthesis
2nano material electrode.
Fig. 3. graphene nanometer sheet/MoS that embodiment 2 is synthetic
2the XRD figure of composite nano materials, graphene nanometer sheet and MoS in composite material
2the ratio of amount be 2: 1.
Fig. 4. the graphene nanometer sheet/MoS of embodiment 2 preparations
2electrochemistry storage lithium capacity and the cycle performance of the Graphene electrodes of composite nano materials electrode and Hydrothermal Synthesis.
(a) graphene nanometer sheet/MoS
2composite nano materials electrode, graphene nanometer sheet and MoS in composite material
2the ratio of amount be 2: 1;
(b) the graphene nano plate electrode of Hydrothermal Synthesis.
Fig. 5. the graphene nanometer sheet/MoS of embodiment 3 preparations
2electrochemistry storage lithium capacity and the cycle performance of composite nano materials electrode, graphene nanometer sheet and MoS in composite material
2the ratio of amount be 4: 1.
Fig. 6. the graphene nanometer sheet/MoS of embodiment 4 preparations
2electrochemistry storage lithium capacity and the cycle performance of composite nano materials electrode, graphene nanometer sheet and MoS in composite material
2the ratio of amount be 3: 1.
Embodiment
Embodiment 1:
The preparation method of the lithium ion cell electrode of a kind of high power capacity and stable cycle performance: the 1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, 2.5mmol (0.03g) 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 25 minutes, temperature rises to 30 ℃ of left and right, adds 45ml deionized water, stirs 20 minutes, adds the H of 12ml 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) 2.5mmol (0.606g) molybdic acid is received and is dissolved in 63ml deionized water, form the solution of 0.04M, add the thiocarbamide of 12.5mmol to stir, thiocarbamide is 5.0: 1 with the ratio of the amount of sodium molybdate, then by the 1st) the prepared graphite oxide nanometer sheet of graphite of 2.5mmol for step (0.03g) adds in this solution, the amount of substance of graphite raw material used is 1: 1 with Molybdenum in Solution acid sodium amount ratio, 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 240 ℃, hydro-thermal reaction is 24 hours, naturally cooling, centrifugation, with deionized water, fully wash rear collection dry, obtain graphene nanometer sheet/MoS
2composite nano materials, SEM, EDX and XRD analysis show that composite material is graphene nanometer sheet/MoS
2composite nano materials, graphene nanometer sheet and MoS in composite nano materials
2the ratio of amount be 1: 1.XRD and SEM figure are shown in Fig. 1.
3) with the above-mentioned graphene nanometer sheet/MoS making
2composite nano materials (graphene nanometer sheet and MoS
2the ratio of amount be 1: 1) 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%.
With lithium paper tinsel, as to electrode and reference electrode, electrolyte is 1.0MLiPF
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.The test result of electrode electro Chemical performance is shown in Fig. 1 (a).
As a comparative example, with 0.3g sodium molybdate and 0.4g thioacetamide, be dissolved in 80ml deionized water, with hydrothermal method, synthesized MoS
2nano material.With XRD to MoS
2nano material characterizes, and result shows that the product of Hydrothermal Synthesis is the MoS of low-crystallinity
2.With the synthetic MoS of gained
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.Test result is shown in Fig. 1 (b).
As can be seen from Figure 2, with graphene nanometer sheet/MoS
2electrode prepared by composite nano materials, its initial reversible capacity reaches 1000mAh/g, and 50 later its capacity that circulate are 1011mAh/g; And with the MoS of Hydrothermal Synthesis
2nano material is electrode prepared by active material, and its initial reversible capacity reaches 835mAh/g, but circulation 50 times after its capacity loss to 613mAh/g.Graphene nanometer sheet/MoS is described
2composite nano materials electrode compares MoS
2nano material electrode has higher specific capacity and better cyclical stability.
Embodiment 2:
The preparation method of the lithium ion cell electrode of a kind of high power capacity and stable cycle performance: the 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 30 ℃ of left and right, adds 45ml deionized water, stirs 20 minutes, adds the H of 10ml 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) 1.25mmol (0.303g) molybdic acid is received and is dissolved in 63ml deionized water, form the solution of 0.02M, add the thioacetamide of 10mmol to stir, wherein thioacetamide is 8: 1 with the ratio of the amount of sodium molybdate, then by the 1st) the prepared graphite oxide nanometer sheet of graphite of 2.5mmol for step (0.03g) adds in this solution, the amount of substance of graphite raw material used is 2: 1 with Molybdenum in Solution acid sodium amount ratio, 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 220 ℃, hydro-thermal reaction is 28 hours, naturally cooling, centrifugation, with deionized water, fully wash rear collection dry, obtain graphene nanometer sheet/MoS
2composite nano materials, SEM, EDX and XRD analysis show that composite material is graphene nanometer sheet/MoS
2composite nano materials, graphene nanometer sheet and MoS in composite nano materials
2the ratio of amount be 2: 1.XRD and SEM figure are shown in Fig. 3.
3) with resulting graphene nanometer sheet/MoS
2composite nano materials (graphene nanometer sheet and MoS
2the ratio of amount be 2: 1) be active material, press the method preparation work electrode of embodiment 1, wherein the mass percentage content of each component is: nano composite material active material 85%, acetylene black 5%, Kynoar 10%, and be assembled into test battery and carry out the test of electrode performance by the method for embodiment 1.Test result is shown in Fig. 4 (a).
As a comparison, the thioacetamide 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 220 ℃, 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.Test result is shown in Fig. 4 (b).
Fig. 4 shows with graphene nanometer sheet/MoS
2composite nano materials (graphene nanometer sheet and MoS
2the ratio of amount be 2: 1) electrode prepared, its initial reversible capacity is 1250mAh/g, its capacity after 50 times that circulate are 1150mAh/g; And the electrode of preparing with graphene nanometer sheet, its initial reversible capacity is 900mAh/g, 50 later its capacity that circulate are 750mAh/g.Presentation of results graphene nanometer sheet/MoS
2composite nano materials electrode has higher specific capacity and better cyclical stability than graphene nano plate electrode.
Embodiment 3:
The preparation method of the lithium ion cell electrode of a kind of high power capacity and stable cycle performance: the 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 3.5 times of graphite, stir 60 minutes, temperature rises to 45 ℃ of left and right, adds 50ml deionized water, stirs 30 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) 1.25mmol (0.303g) molybdic acid is received and is dissolved in 63ml deionized water, form the solution of 0.02M, add the thioacetamide of 15mmol to stir, thioacetamide is 12: 1 with the ratio of the amount of sodium molybdate, then by the 1st) the prepared graphite oxide nanometer sheet of graphite of 5.0mmol for step (0.06g) adds in this solution, the amount of substance of graphite raw material used is 4: 1 with Molybdenum in Solution acid sodium amount ratio, 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 230 ℃, hydro-thermal reaction is 30 hours, naturally cooling, centrifugation, with deionized water, fully wash rear collection dry, obtain graphene nanometer sheet/MoS
2composite nano materials, SEM, EDX and XRD analysis show that composite material is graphene nanometer sheet/MoS
2composite nano materials, graphene nanometer sheet and MoS in composite nano materials
2the ratio of amount be 4: 1.
3) by resulting graphene nanometer sheet/MoS
2composite nano materials (graphene nanometer sheet and MoS
2the ratio of amount be 4: 1) be active material, press the method preparation work electrode of embodiment 1, wherein the mass percentage content of each component is: nano composite material active material 75%, acetylene black 10%, Kynoar 15%, and be assembled into test battery and carry out the test of electrode performance by the method for embodiment 1.Test result is shown in Fig. 3.
Fig. 5 shows with graphene nanometer sheet/MoS
2composite nano materials (graphene nanometer sheet and MoS
2the ratio of amount be 4: 1) electrode prepared, its initial reversible capacity is 1105mAh/g, circulating and playing capacity 50 times is later 1055mAh/g.Presentation of results graphene nanometer sheet/MoS
2composite nano materials electrode electrode has high specific capacity and excellent cyclical stability.
Embodiment 4:
The preparation method of the lithium ion cell electrode of a kind of high power capacity and stable cycle performance: the 1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, 9.0mmol (0.108g) 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 25ml mass concentration 30%
2o
2, stir 25 minutes, through centrifugation, with obtaining graphite oxide nanometer sheet after mass concentration 5%HCl solution, deionized water and acetone cyclic washing;
2) 3.0mmol ammonium molybdate is dissolved in 60ml deionized water, form the solution of 0.05M, add the thiocarbamide of 30mmol to stir, thiocarbamide is 10: 1 with the ratio of the amount of sodium molybdate, then by the 1st) the prepared graphite oxide nanometer sheet of graphite of 9.0mmol for step (0.108g) adds in this solution, the amount of substance X of graphite raw material used is 3: 1 with Molybdenum in Solution acid sodium amount ratio, 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 240 ℃, hydro-thermal reaction is 36 hours, naturally cooling, centrifugation, with deionized water, fully wash rear collection dry, obtain graphene nanometer sheet/MoS
2composite nano materials, SEM, EDX and XRD analysis show that composite material is graphene nanometer sheet/MoS
2composite nano materials, graphene nanometer sheet and MoS in composite nano materials
2the ratio of amount be 3: 1.
2) with resulting graphene nanometer sheet/MoS
2composite nano materials (graphene nanometer sheet and MoS
2the ratio of amount be 3: 1) be active material, press the method preparation work electrode of embodiment 1, wherein the mass percentage content of each component is: nano composite material active material 85%, acetylene black 5%, Kynoar 10%, and be assembled into test battery and carry out the test of electrode performance by the method for embodiment 1.Test result is shown in Fig. 4.
Fig. 6 shows with graphene nanometer sheet/MoS
2composite nano materials (graphene nanometer sheet and MoS
2the ratio of amount be 3: 1) electrode prepared, its initial reversible capacity is 1180mAh/g, circulating and playing capacity 50 times is later 1202mAh/g.Presentation of results graphene nanometer sheet/MoS
2composite nano materials electrode has high specific capacity and excellent cyclical stability.
Claims (2)
1. a lithium ion cell electrode for high power capacity and stable cycle performance, the active material that it is characterized in that this electrode is graphene nanometer sheet/MoS
2composite nano materials, all the other are acetylene black and Kynoar, and the mass percentage content of each component is: nano composite material active material 75-85%, acetylene black 5-10%, Kynoar 5-15%, graphene nanometer sheet and MoS in composite nano materials active material wherein
2the ratio of the amount of nano material is 1: 1～4: 1;
The preparation method of the lithium ion cell electrode of high power capacity and stable cycle performance, it comprises the following steps:
1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, 0.015-0.12g 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 20-60 minute, temperature rises to 30-35 ℃, adds 46ml deionized water, stirs 20-30 minute, adds the H of 10-15ml mass concentration 30%
2o
2, stir 5-10 minute, through centrifugation, after solution, deionized water and acetone cyclic washing with mass concentration 5%HCl, obtain graphite oxide nanometer sheet;
2) molybdate is dissolved in to the solution that forms 0.02～0.05M in deionized water, add thioacetamide or thiocarbamide as sulphur source and reducing agent, thioacetamide or thiocarbamide are 5: 1～12: 1 with the ratio of the amount of molybdate, again by by the 1st) the graphite oxide nanometer sheet for preparing of step adds in this solution, the 1st) ratio of the amount of step graphite raw material used and the amount of molybdate is 1: 1～4: 1, ultrasonic processing 1-2h, graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, this mixture is proceeded in the hydrothermal reaction kettle of inner liner polytetrafluoroethylene and seal, at 220-250 ℃ of reaction 24-36h, the product obtaining is through centrifugation, and with deionized water and absolute ethanol washing, dry, obtain graphene nanometer sheet/MoS
2composite nano materials,
3) by graphene nanometer sheet/MoS
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 75～85%, acetylene black 5～10%, Kynoar 5-15%, this pastel is coated onto equably on the Copper Foil of collector, vacuumize, roll extrusion obtains electrode.
2. the lithium ion cell electrode of a kind of high power capacity according to claim 1 and stable cycle performance, is characterized in that molybdate is sodium molybdate or ammonium molybdate.
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| CN102142541B true CN102142541B (en) | 2014-08-13 |
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