CN102142541A - 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
2Composite nano materials belongs to the field of mechanism of new electrochemical power sources and new energy materials as the electrode of the lithium ion battery with high power capacity and stable cycle performance of electroactive substance preparation.
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).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 graphene nano chip architecture unstable or reunite in inappropriate arrangement of graphene nanometer sheet and the electrode production process and in the charge and discharge process.
On the other hand, MoS
2Having typical sandwich layer structure, is covalent bonds in the layer of S-Mo-S, then mutually combines with more weak Van der Waals force between layer and the layer, 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
2More weak interlaminar action power and bigger interlamellar spacing allow to be reflected 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
2Be a kind of rising electrochemical lithium storage that is used for heavy-duty battery and electrode material [G.X.Wang, S.Bewlay, J.Yao, et al., Electrochem.Solid State, 2004, the 7:A321 of 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
2Electrochemistry embedding lithium and take off the lithium performance (Y.Miki, D.Nakazato, H.Ikuta, et al., J.Power Sources, 1995,54:508), found that the amorphous MoS that they synthesize
2In the powder, the reversible capacity of the electrochemistry doff lithium of the sample that performance is best has only 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.The hydrothermal method that [J.Alloys Compounds, 2009,471 (1-2): 442-447] such as nearest Li assist with ionic liquid has synthesized the MoS of floriform appearance
2, its electrochemistry storage lithium reversible capacity reaches 850mAh/g, but their cycle performance of report is still not good enough, remains further to be improved.
In sum, graphene nanometer sheet and MoS
2Nano material all is a good electrochemistry storage lithium electrode material, 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 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, 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 MoS in addition
2Compound, the big ∏ key and the MoS 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 MoS
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/MoS
2Nano composite material yet there are no open report as electrochemistry embedding/lithium ionic insertion/deinsertion electrode that electroactive substance prepares the lithium ion battery with high power capacity and high stable circulation performance.
Summary of the invention
The object of the present invention is to provide the 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 the 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 may further comprise the steps:
1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, the 0.015-0.12g 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 20-60 minute, temperature rises to about 30-35 ℃, adds the 46ml deionized water, stirs the H of adding 10-15ml mass concentration 30% 20-30 minute
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) molybdate is dissolved in the solution that forms 0.02～0.05M in the 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 will be by the 1st) step adds in this solution with 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, 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 200-240 ℃ of reaction 24-36h, the product centrifugation that obtains, and with deionized water and absolute ethanol washing, drying obtains graphene nanometer sheet/MoS
2Composite nano materials.
3) with 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 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 5-15%, this pastel is coated onto on the Copper Foil as collector equably, 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) because graphene nanometer sheet and MoS
2Have typical sheet or layer structure, the both is good electrochemistry storage lithium electrode material, lithium ion battery negative material as a new generation has good application prospects, but their electrochemistry storage lithium capacity and stable circulation performance are still waiting further raising.If with graphene nanometer sheet and MoS
2The compound preparation composite nano materials 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 MoS in addition
2Compound, the big ∏ key and the MoS 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 MoS
2Interlamellar spacing, the electrochemistry of the suitable favourable reinforced composite of interlamellar spacing structure storage lithium performance.
2) the present invention prepares graphene nanometer sheet/MoS
2In the process of composite nano materials, become graphene nanometer sheet, and be compounded to form composite material with molybdenum disulfide nano material that the original position hydro-thermal reaction forms by graphite oxide nanometer sheet in-situ reducing.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, 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 molybdate the surface of graphite oxide nanometer sheet by complexing, can make generated in-situ graphene nanometer sheet and molybdenum disulfide nano material height ground evenly compound in the reproducibility hydrothermal reaction process better.
3) the present invention is a raw material with stannic oxide/graphene nano sheet and molybdate, thioacetamide or thiocarbamide, adopts original position hydrothermal reduction method one to go on foot the nano composite material that has become out graphene nanometer sheet/molybdenum bisuphide.Synthetic 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 MoS in the composite Nano material
2Mutual synergy between the nano material, the present invention graphene nanometer sheet/MoS
2Composite nano materials is that the electrode of electroactive substance preparation compares MoS
2Nano material and graphene nano plate electrode have higher electrochemistry storage lithium reversible capacity and better stable circulation performance.In the lithium ion battery of a new generation, have widely and use.
Description of drawings
Fig. 1. graphene nanometer sheet/MoS that embodiment 1 synthesizes
2The XRD figure of composite nano materials and SEM pattern, graphene nanometer sheet and MoS in the composite material
2The ratio of amount be 1: 1.
Fig. 2. graphene nanometer sheet/MoS of embodiment 1
2The MoS that composite nano materials electrode and hydro-thermal are synthetic
2The electrochemistry storage lithium capacity and the cycle performance of nano material electrode.
(a) graphene nanometer sheet/MoS
2The composite nano materials electrode, graphene nanometer sheet and MoS in the composite material
2The ratio of amount be 1: 1;
(b) the synthetic MoS of hydro-thermal
2The nano material electrode.
Fig. 3. graphene nanometer sheet/MoS that embodiment 2 synthesizes
2The XRD figure of composite nano materials, graphene nanometer sheet and MoS in the composite material
2The ratio of amount be 2: 1.
Fig. 4. the graphene nanometer sheet/MoS of embodiment 2 preparations
2The electrochemistry storage lithium capacity and the cycle performance of the Graphene electrodes that composite nano materials electrode and hydro-thermal are synthetic.
(a) graphene nanometer sheet/MoS
2The composite nano materials electrode, graphene nanometer sheet and MoS in the composite material
2The ratio of amount be 2: 1;
(b) the synthetic graphene nano plate electrode of hydro-thermal.
Fig. 5. the graphene nanometer sheet/MoS of embodiment 3 preparations
2The electrochemistry storage lithium capacity and the cycle performance of composite nano materials electrode, graphene nanometer sheet and MoS in the composite material
2The ratio of amount be 4: 1.
Fig. 6. the graphene nanometer sheet/MoS of embodiment 4 preparations
2The electrochemistry storage lithium capacity and the cycle performance of composite nano materials electrode, graphene nanometer sheet and MoS in the 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, stirs adding 0.03g KMnO down
4, institute adds KMnO
4Quality be 3 times of graphite, stirred 25 minutes, temperature rises to about 30 ℃, adds the 45ml deionized water, stirs the H of adding 12ml 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) 2.5mmol (0.606g) molybdic acid is received be dissolved in the 63ml deionized water, form the solution of 0.04M, the thiocarbamide that adds 12.5mmol stirs, thiocarbamide is 5.0: 1 with the ratio of the amount of sodium molybdate, then with the 1st) step add in this solution with the prepared graphite oxide nanometer sheet of the graphite of 2.5mmol (0.03g), sodium molybdate 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 240 ℃ of following hydro-thermal reactions 24 hours, natural cooling, centrifugation is fully washed the back with deionized water and is collected also drying, obtains 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 the composite nano materials
2The ratio of amount be 1: 1.XRD and SEM figure see Fig. 1.
3) with the above-mentioned graphene nanometer sheet/MoS that makes
2Composite nano materials (graphene nanometer sheet and MoS
2The ratio of amount be 1: 1) 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%.
To electrode and reference electrode, electrolyte is 1.0MLiPF with the conduct of lithium paper tinsel
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.The test result of electrode electro Chemical performance is seen Fig. 1 (a).
As a comparative example, be dissolved in the 80ml deionized water, synthesized MoS with hydrothermal method with 0.3g sodium molybdate and 0.4g thioacetamide
2Nano material.With XRD to MoS
2Nano material characterizes, and the result shows that the synthetic product of hydro-thermal is the MoS of low-crystallinity
2With 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 seen Fig. 1 (b).
As can be seen from Figure 2, with graphene nanometer sheet/MoS
2The electrode of composite nano materials preparation, its initial reversible capacity reaches 1000mAh/g, and 50 later its capacity that circulate are 1011mAh/g; And the MoS of water thermal synthesis
2Nano material is the electrode of active material preparation, and its initial reversible capacity reaches 835mAh/g, but its capacity drops to 613mAh/g after circulation 50 times.Graphene nanometer sheet/MoS is described
2The composite nano materials electrode compares MoS
2The nano 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, stirs adding KMnO down
4, institute adds KMnO
4Quality be 4 times of graphite, stirred 40 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 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) 1.25mmol (0.303g) molybdic acid is received be dissolved in the 63ml deionized water, form the solution of 0.02M, the thioacetamide that adds 10mmol stirs, wherein thioacetamide is 8: 1 with the ratio of the amount of sodium molybdate, then with the 1st) step add in this solution with the prepared graphite oxide nanometer sheet of the graphite of 2.5mmol (0.03g), sodium molybdate 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 220 ℃ of following hydro-thermal reactions 28 hours, natural cooling, centrifugation is fully washed the back with deionized water and is collected also drying, obtains 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 the composite nano materials
2The ratio of amount be 2: 1.XRD and SEM figure see 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 seen Fig. 4 (a).
As a comparison, the thioacetamide 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 220 ℃ 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.Test result is seen 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 of preparation, its initial reversible capacity is 1250mAh/g, 50 later its capacity that circulates are 1150mAh/g; And with the electrode of graphene nanometer sheet preparation, its initial reversible capacity is 900mAh/g, and 50 later its capacity that circulates are 750mAh/g.Presentation of results graphene nanometer sheet/MoS
2The composite 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, stirs adding KMnO down
4, institute adds KMnO
4Quality be 3.5 times of graphite, stirred 60 minutes, temperature rises to about 45 ℃, adds the 50ml deionized water, stirs the H of adding 20ml mass concentration 30% 30 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) 1.25mmol (0.303g) molybdic acid is received be dissolved in the 63ml deionized water, form the solution of 0.02M, the thioacetamide that adds 15mmol stirs, thioacetamide is 12: 1 with the ratio of the amount of sodium molybdate, then with the 1st) step add in this solution with the prepared graphite oxide nanometer sheet of the graphite of 5.0mmol (0.06g), sodium molybdate 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 230 ℃ of following hydro-thermal reactions 30 hours, natural cooling, centrifugation is fully washed the back with deionized water and is collected also drying, obtains 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 the composite nano materials
2The ratio of amount be 4: 1.
3) with 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 seen 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 of preparation, its initial reversible capacity is 1105mAh/g, circulate 50 times later on a capacity be 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, 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 25ml mass concentration 30% 30 minutes
2O
2, stirred 25 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 3.0mmol ammonium molybdate is dissolved in the 60ml deionized water, form the solution of 0.05M, the thiocarbamide that adds 30mmol stirs, thiocarbamide is 10: 1 with the ratio of the amount of sodium molybdate, then with the 1st) step add in this solution with the prepared graphite oxide nanometer sheet of the graphite of 9.0mmol (0.108g), sodium molybdate amount ratio is 3: 1 in the amount of substance X 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 240 ℃ of following hydro-thermal reactions 36 hours, natural cooling, centrifugation is fully washed the back with deionized water and is collected also drying, obtains 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 the 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 seen 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 of preparation, its initial reversible capacity is 1180mAh/g, circulate 50 times later on a capacity be 1202mAh/g.Presentation of results graphene nanometer sheet/MoS
2The composite nano materials electrode has high specific capacity and excellent cyclical stability.
Claims (3)
1. the lithium ion cell electrode of 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 the nano composite material active material wherein
2The ratio of the amount of nano material is 1: 1～4: 1.
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 the preparation method may further comprise the steps:
1) preparation of graphite oxide nanometer sheet: under 0 ℃ of ice bath, the 0.015-0.12g 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 20-60 minute, temperature rises to about 30-35 ℃, adds the 46ml deionized water, stirs the H of adding 10-15ml mass concentration 30% 20-30 minute
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) molybdate is dissolved in the solution that forms 0.02～0.05M in the 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 will be by the 1st) the graphite oxide nanometer sheet for preparing of step adds in this solution, the 1st) amount of used graphite raw material of step is 1: 1～4: 1 with the ratio of the amount of molybdate, 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 220-250 ℃ of reaction 24-36h, the product centrifugation that obtains, and with deionized water and absolute ethanol washing, drying obtains graphene nanometer sheet/MoS
2Composite nano materials;
3) with 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 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 5-15%, this pastel is coated onto on the Copper Foil as collector equably, vacuumize, roll extrusion obtains electrode.
3. the lithium ion cell electrode of a kind of high power capacity according to claim 2 and stable cycle performance is characterized in that molybdate is sodium molybdate or ammonium molybdate.
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| CN201110046491.XA CN102142541B (en) | 2011-02-25 | 2011-02-25 | High capacity and stable cyclic performance lithium ion battery electrode and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1994896A (en) * | 2006-12-20 | 2007-07-11 | 浙江大学 | Preparation method of one-step hydrothermal synthesis of carbon/molybdenum disulfide composite microsphere |
| US20080048152A1 (en) * | 2006-08-25 | 2008-02-28 | Jang Bor Z | Process for producing nano-scaled platelets and nanocompsites |
| CN101420023A (en) * | 2008-12-11 | 2009-04-29 | 浙江大学 | Electrochemical lithium ionic insertion/deinsertion electrode and production method thereof |
-
2011
- 2011-02-25 CN CN201110046491.XA patent/CN102142541B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080048152A1 (en) * | 2006-08-25 | 2008-02-28 | Jang Bor Z | Process for producing nano-scaled platelets and nanocompsites |
| CN1994896A (en) * | 2006-12-20 | 2007-07-11 | 浙江大学 | Preparation method of one-step hydrothermal synthesis of carbon/molybdenum disulfide composite microsphere |
| CN101420023A (en) * | 2008-12-11 | 2009-04-29 | 浙江大学 | Electrochemical lithium ionic insertion/deinsertion electrode and production method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JONATHAN N. COLEMAN ET AL.: "Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered Materials", 《SCIENCE》, vol. 331, 4 February 2011 (2011-02-04), pages 568 - 571, XP055141317, DOI: doi:10.1126/science.1194975 * |
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