CN102142540B - Lithium ion battery electrode made of graphene/SnS2 composite nanometer material and preparation method thereof - Google Patents

Lithium ion battery electrode made of graphene/SnS2 composite nanometer material and preparation method thereof Download PDF

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CN102142540B
CN102142540B CN201110046456.8A CN201110046456A CN102142540B CN 102142540 B CN102142540 B CN 102142540B CN 201110046456 A CN201110046456 A CN 201110046456A CN 102142540 B CN102142540 B CN 102142540B
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graphene
sns
electrode
nano materials
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CN102142540A (en
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陈卫祥
常焜
陈涛
马琳
李�赫
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Zhejiang University ZJU
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Abstract

The invention discloses a lithium ion battery electrode made of a graphene/SnS2 composite nanometer material and a preparation method thereof. The lithium ion battery electrode is characterized in that the active substance of the electrode is the graphene/SnS2 composite nanometer material, and the other components of the electrode are acetylene black and polyvinylidene fluoride. The lithium ion battery electrode comprises the following components in percentage by weight: 75-85% of the composite nanometer material active substance, 5-10% of the acetylene black and 10% of the polyvinylidene fluoride; and the mass ratio of the graphene to SnS2 nanometer material in the composite nanometer material active substance is (1:1)-(4:1). The electrode preparation method disclosed by the invention comprises the following steps: preparing a graphite oxide nanometer sheet by taking graphite as a raw material by virtue of a chemical oxidation method; in the presence of the graphite oxide nanometer sheet, synthetizing to obtain the graphene/SnS2 composite nanometer material by virtue of a one-step hydrothermal in-situ reduction method; and finally, taking the graphene/SnS2 composite nanometer material as the active substance to prepare the electrode. The electrode disclosed by the invention has the advantages of higher electrochemical lithium storage capacity and excellent cyclical stability and can be widely used in the new generation of lithium ion batteries.

Description

Graphene/SnS 2lithium ion cell electrode of composite nano materials and preparation method thereof
Technical field
The present invention relates to lithium ion cell electrode and preparation method thereof, relate in particular to Graphene/SnS 2composite nano materials is the high power capacity prepared of active material and the lithium ion cell electrode of stable cycle performance, belongs to mechanism of new electrochemical power sources and preparing technical field thereof.
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 such as mobile phone and notebook computer electrical equipment.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.Capacity and the stable circulation performance of a new generation's lithium ion battery to electrode material had higher requirement, and 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 the 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.Graphene nanometer sheet has high specific area, high conduction and heat conductivility, superpower mechanical property.Recently people have carried out research widely to graphene nanometer sheet as the application of the electrode material of micro-nano electronic device, new forms of energy battery, kollag and novel catalyst carrier.
SnS 2have layered crystal structure, it forms octahedral coordination by two-layer compact arranged S atom and the sandwich sandwich structure forming of Sn cation, combines between layers with weak Van der Waals force.SnS 2there is good electrochemistry seasoning lithium performance as lithium ion battery negative material.SnS 2electrochemical lithiation theoretical capacity be 645mAh/g, so the theoretical capacity of large graphite 372mAh/g.Therefore, SnS 2can be used as a kind of potential lithium ion battery negative material of alternative graphite material.[Momma T, ShiraishiN, Yoshizawa A, et al., the SnS such as Momma 2anode for rechargeable lithium battery.Journal of PowerSources, 2001,97-98:198～200] use SnCl 4the SnS synthetic with thioacetamide method 2product is after 400 DEG C of processing, and its electrochemistry storage lithium reversible capacity reaches 600mAh/g, but after circulation 25 times, capacity is less than 400mAh/g.Therefore, its cycle performance is to be further improved in addition.[Seo JW, Jang JT, Park SW, et al., the Two-Dimensional SnS such as Seo JW 2nanoplates with Extraordinary HighDischarge Capacity for Lithium Ion Batteries.Advanced Materials.2008,20 (22): 4269～4273] by by organic Sn presoma pyrolyzing synthesis SnS 2nanocrystal, result shows SnS 2more than the electrochemistry storage lithium capacity of nanocrystal can reach 600mAh/g, and there is good stable circulation performance, shown SnS 2nanocrystal has a good application prospect as lithium ion battery negative material.
Due to graphene nanometer sheet and SnS 2it is all the electrode material of very promising new forms of energy battery.If graphene nanometer sheet and SnS 2the corresponding composite nano materials of the compound preparation of nano material, the high conduction performance of graphene nanometer sheet can further improve the electric conductivity of composite material, be conducive to the electronics transmission in electrochemical electrode reaction and catalytic reaction process, the chemical property of reinforced composite electrode.Graphene nanometer sheet and SnS in addition 2compound, due to large ∏ key and the SnS of graphene nanometer sheet 2the interaction of Electronic Structure, can form the electronic structure between a kind of new different material.This graphene nanometer sheet and SnS 2the performance that composite nano materials has having a wide range of applications and strengthens as new forms of energy electrode material.But with graphene nanometer sheet and SnS 2the research that composite nano materials is prepared lithium ion cell electrode as active material have not been reported.
The application of biological micromolecule in nano material is synthetic recently obtained people's extensive concern.Cys contains multiple functional group (as: NH 2,-COOH and-SH), these functional groups can provide coordination atom and metal cation to form coordinate bond.Cys has obtained application in synthetic transient metal sulfide nano material.Document [Zhang B, Ye XC, Hou WY, Zhao Y, Xie Y.Biomolecule-assistedsynthesis and electrochemical hydrogen storage of Bi 2s 3flowerlike patterns withwell-aligned nanorods.Journal of Physical Chemistry B, 2006,110 (18) 8978～8985] synthesized the Bi of floriform appearance with Cys 2s 3nano structural material.But up to the present, come synthesizing graphite alkene and SnS with Cys 2composite nano materials, and with Graphene and SnS 2composite nano materials as active material prepare lithium ion cell electrode research yet there are no publicly report.
Summary of the invention
The object of the present invention is to provide a kind of Graphene/SnS 2lithium ion cell electrode of composite nano materials and preparation method thereof, the active material that it is characterized in that this electrode is Graphene and SnS 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 10%, wherein, Graphene and SnS in nano composite material active material 2between nano material, the ratio of amount is 1: 1-4: 1.
Graphene/SnS of the present invention 2the lithium ion cell electrode of composite nano materials, is characterized in that preparation method comprises the following steps:
1) preparation of graphite oxide nanometer sheet: under 0 DEG C of ice bath, 0.015-0.072g graphite powder is distributed in the 20-25mL concentrated sulfuric acid, adds KMnO under stirring 4, institute adds KMnO 4quality be graphite 3-4 doubly, stir 30-60 minute, temperature rise, to 30-35 DEG C of left and right, adds 40-50ml deionized water, stirs 20-30 minute, adds the H of 10-15ml mass concentration 30% 2o 2, stir 5-20 minute, through centrifugation, with obtaining graphite oxide nanometer sheet after mass concentration 5%HCl solution, deionized water and acetone cyclic washing;
2) Cys is dissolved in deionized water, then adds butter of tin (SnCl 45H 2o) and fully stir and make its dissolving, in solution, the mol ratio of Cys and butter of tin was at 6: 1～12: 1, again will be by the 1st) the preparation-obtained graphite oxide nanometer sheet of step adds in this solution, the 1st) step graphite raw material amount used is 1: 1～4: 1 with the ratio of the amount of butter of tin, 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 180-200 DEG C of reaction 20-36h, the product centrifugation obtaining, and with deionized water and absolute ethanol washing, dry, obtain Graphene and SnS 2composite nano materials,
3) by Graphene and SnS 2composite nano materials as the active material of electrode, under agitation fully mix the uniform pastel of furnishing with the 1-METHYLPYRROLIDONE solution of the Kynoar of acetylene black and mass concentration 5%, each constituent mass percentage is: nano composite material active material 75-85%, acetylene black 5-10%, Kynoar 10%, this pastel is coated onto equably on the Copper Foil of collector, vacuumize, roll extrusion obtains electrode.
Method of the present invention has reaction condition gentleness and the simple feature of technique.Synthesizing graphite alkene of the present invention and SnS 2composite nano materials have a wide range of applications as the electrode material of new forms of energy battery lithium ion battery, electrochemistry storage Development of Magnesium Electrode Materials, kollag and catalyst carrier.
Method of the present invention has advantages of following outstanding compared with the prior art:
(1) because Graphene has high specific area, superpower mechanical property, the high excellent properties such as conduction and heat conduction, therefore, Graphene of the present invention and SnS 2composite nano materials there is mechanical property, conduction and the heat conductivility of enhancing, be conducive to it as the electronics transmission in electrode reaction, the catalytic reaction process of new forms of energy battery electrode material, strengthen chemical property and the catalytic performance of composite nano materials.And the superpower mechanical property of Graphene has also strengthened the mechanical property of composite nano materials, can improve its tribological property as kollag.Graphene and SnS in addition 2compound, due to large ∏ key and the SnS of Graphene 2the interaction of Electronic Structure, can form the electronic structure between a kind of new different material, and the electrons height delocalization of participation role, is conducive to the quick transmission of electronics in electrochemical reaction process.This Graphene and SnS 2composite nano materials have a wide range of applications and strengthen the performance of improvement as electrode material electrochemistry storage lithium, electrochemistry storage magnesium and catalyst carrier etc.
(2) the present invention's graphene oxide, and butter of tin, Cys are raw material, adopt Situ Hydrothermal reducing process to become out Graphene and SnS 2composite nano materials.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.
(3) in course of reaction of the present invention, graphene oxide in-situ reducing becomes Graphene, and react with Situ Hydrothermal form stannic disulfide nano material be compounded to form composite material.Its advantage is: graphite oxide nanometer sheet contains abundant oxygen-containing functional group (as: hydroxyl, carbonyl and carboxyl etc.), in hydro-thermal reaction solution, after ultrasonic dispersion, no longer easily again reunited or be deposited in together, and the functional group on graphite oxide surface can be adsorbed on tin ion the surface of graphite oxide nanometer sheet by complexing, in reproducibility hydrothermal reaction process, can be generated in-situ Graphene and SnS 2nano material height is evenly compound.
(4) Cys contains multiple functional group (as: NH 2,-COOH and-SH), these functional groups can provide coordination atom and ion to form coordinate bond.Therefore, Cys can with solution in tin ion ion form coordination.Due to the existence of graphene oxide in solution, just formed the coordination mode of graphene oxide-tin ion-Cys, can be generated in-situ Graphene and SnS simultaneously in reproducibility hydrothermal reaction process 2nano material height is compound nano material evenly.
(5) synthesizing graphite alkene of the present invention and SnS 2the method of composite nano materials be also advantageous in that: by adjusting the ratio of synthetic solvent Raw, can obtain Graphene and the SnS of different proportion 2composite nano materials, Graphene and SnS 2the difference of nano material ratio can be adjusted SnS 2the degree of crystallinity of nano material, makes the application of its applicable different field.
(4) existence of graphene nanometer sheet in the intermediate product in preparation process, can suppress the excessive crystal growth of stannic disulfide in heat treatment process and reunite, obtain the less stannic disulfide nano material of the lower and number of plies of relative crystallinity and the composite nano materials of graphene nanometer sheet, such composite nano materials has high electrochemistry and stores lithium capacity and overstable cycle performance.
(3) method of the present invention has reaction condition gentleness, and technique is simple, the advantage of the high and favorable reproducibility of productive rate.Due to graphene nanometer sheet and SnS 2synergy, graphene nanometer sheet and SnS for the present invention 2the electrode of the lithium ion battery prepared of the composite nano materials active material that is electrode there is high electrochemistry storage lithium capacity and overstable cycle performance.
Brief description of the drawings
Fig. 1 Graphene and SnS 2the SEM of composite nano materials and TEM pattern.
(a) SnS that prepared by embodiment 1 2the SEM of nano material and TEM pattern;
(b) embodiment 1 prepares Graphene and SnS 2the SEM of composite nano materials and TEM pattern, Graphene and SnS 2the ratio of amount is 2: 1.
Fig. 2 Graphene and SnS 2the XRD figure of composite nano materials.
(a) XRD of the synthetic Graphene of embodiment 1 comparative example;
(b) Graphene and the SnS that prepared by embodiment 1 2the XRD figure of composite nano materials, Graphene and SnS 2the ratio of amount is 2: 1;
(c) the synthetic SnS of embodiment 1 comparative example 2the XRD figure of nano material.
Fig. 3 Graphene/SnS 2composite nano materials electrode, Graphene electrodes and SnS 2the charge/discharge capacity of nano material electrode and cycle performance.
(a) Graphene/SnS that prepared by embodiment 1 2composite nano materials electrode;
(b) Graphene electrodes that prepared by embodiment 1;
(c) SnS that prepared by embodiment 1 2nano material electrode.
Embodiment
Embodiment 1:
Graphene/SnS 2the lithium ion cell electrode preparation method of composite nano materials: the 1) preparation of graphite oxide nanometer sheet: under 0 DEG C of ice bath, 4.0mmol (0.048g) graphite powder is distributed in the 20mL concentrated sulfuric acid, adds 0.03g KMnO under stirring 4, institute adds KMnO 4quality be 3 times of graphite, stir 30 minutes, temperature rise to 30 DEG C left and right, adds 45ml deionized water, stirs 20 minutes, adds the H of 10ml mass concentration 30% 2o 2, stir 5 minutes, through centrifugation, with obtaining graphite oxide nanometer sheet after mass concentration 5%HCl solution, deionized water and acetone cyclic washing;
2) 1.94g (16mmol) Cys is dissolved in 160ml deionized water, then adds 0.70g (2mmol) butter of tin (SnCl 45H 2o), and stir make its dissolve, Cys and SnCl in mixed solution 4mol ratio be 8: 1.Then by the 1st) the prepared graphite oxide nanometer sheet of graphite of 4.0mmol for step (0.048g) adds in this solution, in the amount of substance of graphite raw material used and solution, the amount ratio of butter of tin is 2: 1, ultrasonic processing 1.0h, graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, then this mixture is transferred in hydrothermal reaction kettle, hydro-thermal reaction 12 hours at 180 DEG C, naturally cooling, centrifugation, fully wash rear collection dry with deionized water, obtain Graphene and SnS 2composite nano materials, Graphene and SnS in composite nano materials 2the ratio of amount be 2: 1.SEM and XRD analysis show that composite material is Graphene and SnS 2composite nano materials.SEM and XRD figure are shown in respectively Fig. 1 and Fig. 2.
3) with the above-mentioned Graphene making and SnS 2composite nano materials (Graphene and SnS 2the ratio of amount be 2: 1) prepare electrode as electroactive substance, composite nano materials 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 DEG C, 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 1.0M LiPF 6eC/DMC solution (1: 1in volume), barrier film is polypropylene film (Celguard-2300), in the suitcase that is full of argon gas, is assembled into test battery.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. 3.
As a comparison, Graphene and SnS have been synthesized respectively with similar hydrothermal method 2nano material, has carried out characterizing (seeing Fig. 1 and Fig. 2) with SEM and XRD, and has prepared as stated above Graphene electrodes and SnS 2nano material electrode, has assembled test battery, has carried out the test of charge-discharge performance, and test result is shown in Fig. 3.
As can be seen from Figure 3, with Graphene and SnS 2electrode prepared by nano material, its initial reversible capacity is 912mAh/g, is 925mAh/g at 50 later its capacity of circulation; And with the SnS of Hydrothermal Synthesis 2nano material is the electrode of active material, and its initial reversible capacity is 470mAh/g, and 50 later its capacity loss that circulate are to 180mAh/g; Graphene is the electrode of active material, and its initial reversible capacity is 670mAh/g, and 50 later its capacity loss that circulate, to 440mAh/g, illustrate Graphene and SnS 2electrode prepared by nano material compares SnS 2nano material electrode and Graphene electrodes have higher specific capacity and better cyclical stability.
Embodiment 2:
Graphene/SnS 2the lithium ion cell electrode preparation method of composite nano materials: the 1) preparation of graphite oxide nanometer sheet: under 0 DEG C of ice bath, 2.0mmol (0.024g) 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 rise to 33 DEG C left and right, adds 50ml deionized water, stirs 25 minutes, adds the H of 12ml mass concentration 30% 2o 2, stir 5-10 minute, through centrifugation, with obtaining graphite oxide nanometer sheet after mass concentration 5%HCl solution, deionized water and acetone cyclic washing;
2) 1.22g (10mmol) Cys is dissolved in 150ml deionized water, then adds 0.70g (2mmol) butter of tin (SnCl 45H 2o), and stir make its dissolve, Cys and SnCl in mixed solution 4mol ratio be 5: 1, then by the 1st) the prepared graphite oxide nanometer sheet of graphite of 2.0mmol for step (0.024g) adds in this solution, in the amount of substance X of graphite raw material used and solution, the amount ratio of butter of tin is 1: 1, ultrasonic processing 1.5h, graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, then this mixture is transferred in hydrothermal reaction kettle, reactor is incubated 16 hours at 190 DEG C, naturally cooling, centrifugation, fully wash rear collection dry with deionized water, obtain Graphene and SnS 2composite nano materials, Graphene and SnS in composite nano materials 2the ratio of amount be 1: 1.SEM and XRD analysis show that composite material is Graphene and SnS 2composite nano materials.
3) with the above-mentioned Graphene making and SnS 2composite nano materials (Graphene and SnS 2the ratio of amount be 1: 1) prepare electrode as electroactive substance, composite nano materials 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 DEG C, 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%.
Press the method assembling test battery of embodiment 1 charge-discharge performance of test electrode, test result shows: Graphene and SnS 2the initial reversible capacity of the electrode of nano material is 832mAh/g, is 839mAh/g at 50 later capacity of circulation, and Graphene and SnS are described 2nano material electrode has high specific capacity and excellent cyclical stability.
Embodiment 3:
Graphene/SnS 2the lithium ion cell electrode preparation method of composite nano materials: the 1) preparation of graphite oxide nanometer sheet: under 0 DEG C of ice bath, 4.5mmol (0.054g) graphite powder is distributed in the 25mL concentrated sulfuric acid, adds KMnO under stirring 4, institute adds KMnO 4quality be 4 times of graphite, stir 50 minutes, temperature rise to 35 DEG C left and right, adds 50ml deionized water, stirs 30 minutes, adds the H of 20ml mass concentration 30% 2o 2, stir 15 minutes, through centrifugation, with obtaining graphite oxide nanometer sheet after mass concentration 5%HCl solution, deionized water and acetone cyclic washing;
2) 1.454g (12mmol) Cys is dissolved in 150ml deionized water, then adds 0.52g (1.5mmol) butter of tin (SnCl 45H 2o), and stir make its dissolve, Cys and SnCl in mixed solution 4mol ratio be 8: 1, then by the 1st) the prepared graphite oxide nanometer sheet of graphite of 4.5mmol for step (0.054g) adds in this solution, in the amount of substance X of graphite raw material used and solution, the amount ratio of butter of tin is 3: 1, ultrasonic processing 2.0h, graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, then this mixture is transferred in hydrothermal reaction kettle, reactor is incubated 20 hours at 200 DEG C, naturally cooling, centrifugation, fully wash rear collection dry with deionized water, obtain Graphene and SnS 2composite nano materials, Graphene and SnS in composite nano materials 2the ratio of amount be 3: 1.SEM and XRD analysis show that composite material is Graphene and SnS 2composite nano materials.
3) with the above-mentioned Graphene making and SnS 2composite nano materials (Graphene and SnS 2the ratio of amount be 3: 1) prepare electrode as electroactive substance, composite nano materials 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 DEG C, obtains electrode through roll extrusion after taking-up again.Wherein the mass percentage content of each component is: nano composite material active material 85%, acetylene black 5%, Kynoar 10%.
Press the method assembling test battery of embodiment 1 charge-discharge performance of test electrode, test result shows: Graphene and SnS 2the initial reversible capacity of the electrode of nano material is 863mAh/g, is 852mAh/g at 50 later capacity of circulation, and Graphene and SnS are described 2nano material electrode has high specific capacity and excellent cyclical stability.
Embodiment 4:
Graphene/SnS 2the lithium ion cell electrode preparation method of composite nano materials: the 1) preparation of graphite oxide nanometer sheet: under 0 DEG C of ice bath, 8.0mmol (0.096g) graphite powder is distributed in the 25mL concentrated sulfuric acid, adds KMnO under stirring 4, institute adds KMnO 4quality be 4 times of graphite, stir 52 minutes, temperature rise to 32 DEG C left and right, adds 40ml deionized water, stirs 15 minutes, adds the H of 15ml mass concentration 30% 2o 2, stir 8 minutes, through centrifugation, with obtaining graphite oxide nanometer sheet after mass concentration 5%HCl solution, deionized water and acetone cyclic washing;
1) 2.423g (20mmol) Cys is dissolved in 150ml deionized water, then adds 0.70g (2mmol) butter of tin (SnCl 45H 2o), and stir make its dissolve, Cys and SnCl in mixed solution 4mol ratio be 10: 1, then by the 1st) the prepared graphite oxide nanometer sheet of graphite of 8.0mmol for step (0.096g) adds in this solution, in the amount X of graphite raw material used and solution, the amount ratio of butter of tin is 4: 1, ultrasonic processing 2.0h, graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, then this mixture is transferred in hydrothermal reaction kettle, reactor is incubated 18 hours at 200 DEG C, naturally cooling, centrifugation, fully wash rear collection dry with deionized water, obtain Graphene and SnS 2composite nano materials, Graphene and SnS in composite nano materials 2the ratio of amount be 4: 1.SEM and XRD analysis show that composite material is Graphene and SnS 2composite nano materials.
3) with the above-mentioned Graphene making and SnS 2composite nano materials (Graphene and SnS 2the ratio of amount be 4: 1) prepare electrode as electroactive substance, composite nano materials 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 DEG C, obtains electrode through roll extrusion after taking-up again.Wherein the mass percentage content of each component is: nano composite material active material 85%, acetylene black 5%, Kynoar 10%.
Press the method assembling test battery of embodiment 1 charge-discharge performance of test electrode, test result shows: Graphene and SnS 2the initial reversible capacity of the electrode of nano material is 786mA/g, is 765mAh/g at 50 later capacity of circulation, and Graphene and SnS are described 2nano material electrode has high specific capacity and excellent cyclical stability.
Embodiment 5:
Graphene/SnS 2the lithium ion cell electrode preparation method of composite nano materials: the 1) preparation of graphite oxide nanometer sheet: under 0 DEG C of ice bath, 10.0mmol (0.12g) 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 rise to 33 DEG C left and right, adds 50ml deionized water, stirs 25 minutes, adds the H of 12ml mass concentration 30% 2o 2, stir 5-10 minute, through centrifugation, with obtaining graphite oxide nanometer sheet after mass concentration 5%HCl solution, deionized water and acetone cyclic washing;
2) 1.22g (10mmol) Cys is dissolved in 150ml deionized water, then adds 3.50g (10mmol) butter of tin (SnCl 45H 2o), and stir make its dissolve, Cys and SnCl in mixed solution 4mol ratio be 1: 1, then by the 1st) the prepared graphite oxide nanometer sheet of graphite of 10.0mmol for step (0.12g) adds in this solution, in the amount of substance X of graphite raw material used and solution, the amount ratio of butter of tin is 1: 1, ultrasonic processing 2.0h, graphite oxide nanometer sheet is well dispersed in hydro-thermal reaction solution, then this mixture is transferred in hydrothermal reaction kettle, reactor is incubated 20 hours at 200 DEG C, naturally cooling, centrifugation, fully wash rear collection dry with deionized water, obtain Graphene and SnS 2composite nano materials, Graphene and SnS in composite nano materials 2the ratio of amount be 1: 1.SEM and XRD analysis show that composite material is Graphene and SnS 2composite nano materials.
3) with the above-mentioned Graphene making and SnS 2composite nano materials (Graphene and SnS 2the ratio of amount be 1: 1) prepare electrode as electroactive substance, composite nano materials 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 DEG C, 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%.
Press the method assembling test battery of embodiment 1 charge-discharge performance of test electrode, test result shows: Graphene and SnS 2the initial reversible capacity of the electrode of nano material is 815mAh/g, is 802mAh/g at 50 later capacity of circulation, and Graphene and SnS are described 2nano material electrode has high specific capacity and excellent cyclical stability.

Claims (1)

1. Graphene/SnS 2the lithium ion cell electrode of composite nano materials, the active material that it is characterized in that this electrode is Graphene and SnS 2composite nano materials, all the other are acetylene black and Kynoar, the mass percentage content of each component is: composite nano materials active material 80-85%, acetylene black 5-10%, Kynoar 10%, wherein, Graphene and SnS in composite nano materials active material 2between nano material, the ratio of amount is 1: 1-4: 1;
The preparation method of lithium ion cell electrode comprises the following steps:
1) preparation of graphite oxide nanometer sheet: under 0 DEG C of ice bath, 0.015-0.072g graphite powder is distributed in the 20-25mL concentrated sulfuric acid, adds KMnO under stirring 4, institute adds KMnO 4quality be graphite powder 3-4 doubly, stir 30-60 minute, temperature rise, to 30-35 DEG C, adds 40-50ml deionized water, stirs 20-30 minute, adds the H of 10-15ml mass concentration 30% 2o 2, stir 5-20 minute, through centrifugation, after solution, deionized water and acetone cyclic washing with the HCl of mass concentration 5%, obtain graphite oxide nanometer sheet;
2) Cys is dissolved in deionized water, then add butter of tin and fully stir and make its dissolving, in solution, the mol ratio of Cys and butter of tin was at 6: 1～12: 1, again will be by the 1st) the preparation-obtained graphite oxide nanometer sheet of step adds in this solution, the 1st) step graphite powder amount used is 1: 1～4: 1 with the ratio of the amount of butter of tin, 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 180-200 DEG C of reaction 20-36h, the product centrifugation obtaining, and with deionized water and absolute ethanol washing, dry, obtain Graphene and SnS 2composite nano materials,
3) by Graphene and SnS 2composite nano materials 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 80-85%, acetylene black 5-10%, Kynoar 10%, this pastel is coated onto equably on the Copper Foil of collector, vacuumize, roll extrusion obtains electrode.
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