CN104134783A - Nano-NiS/graphene composite anode material and preparation method thereof - Google Patents
Nano-NiS/graphene composite anode material and preparation method thereof Download PDFInfo
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- CN104134783A CN104134783A CN201410373804.6A CN201410373804A CN104134783A CN 104134783 A CN104134783 A CN 104134783A CN 201410373804 A CN201410373804 A CN 201410373804A CN 104134783 A CN104134783 A CN 104134783A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method of a NiS/graphene composite anode material. The method includes: firstly preparing NiS nanoparticles by a solvothermal method, performing surface modification on the NiS particles by a surfactant, then compounding the modified NiS particles with graphene oxide under electrostatic attraction; and reducing graphene oxide by hydrazine hydrate so as to finally form graphene packaged nano-NiS/graphene composite anode material. The dispersion and packaging effects of graphene on NiS can effectively buffer NiS's volume expansion generated during charging and discharging, and inhibit dissolution of the product in an electrolyte solution in an electrode reaction process, thus improving the cyclic stability of the composite material. At the same time, graphene provides a good conductive network, which is conducive to rapid transmission of electrons, thereby reducing electrode polarization and greatly improving the rate performance of the composite material. The NiS/graphene composite material prepared by the method provided by the invention has excellent electrochemical performance, and the preparation process is simple, the conditions are mild, so that the method is suitable for large-scale industrialized production.
Description
Technical field
The invention belongs to new energy materials and electrochemical field, be specifically related to a kind of novel lithium battery nano nickel sulphide/Graphene (NiS/graphene) composite positive pole and preparation method thereof that discharges and recharges.
Technical background
Current era, lithium battery relies on the advantages such as its high reversible capacity, high voltage, high cycle performance, high-energy-density, long circulation life, little self-discharge rate and memory-less effect, is widely used in fields such as the digital electronic goods such as mobile phone, notebook and hybrid-electric cars.The fast development of electronic digital product, also more and more higher to its battery performance used requirement, the lithium battery that urgent need has high power capacity, high-energy-density meets its market demand.Now, " bottleneck " of restriction lithium battery capacity is positive electrode.All the time, people to this research, there is increase but no decrease in enthusiasm.Sulfur compound positive electrode, with advantages such as its high power capacity, low cost, hypotoxicity, cycle performance are better, becomes and has one of positive electrode of development prospect at present most.Solving electrolytical coupling, suppressing Li dendrite generation and improve on the basis of the problems such as cycle performance, be expected to the energy storage material industrialization this type of excellent performance, therefore have very important significance for the research tool of this type of positive electrode.
Metal sulfide is as FeS
2, CoS
x, MoS
2owing to thering is higher theoretical capacity, be potential anode material of lithium battery with NiS.NiS theoretical capacity is up to 590 mAh/g, aboundresources, and low toxicity, conductivity is better, has been subject in recent years researchers' extensive concern.But NiS is accompanied by larger change in volume in removal lithium embedded process, make active particle generation efflorescence, active material and collector lose and electrically contact or come off from its surface, cause the quick decay of capacity.Meanwhile, enormousness in charge and discharge process changes, and makes the SEI membrane structure that generates unstable, or the unsalted surface being caused by particle fracture react generation SEI film again with electrolyte, causes the cycle efficieny of electrode low.At present, much research is all attempted to improve its chemical property by the whole bag of tricks, as reduces particle size, synthetic special appearance etc.The another kind of method of effectively improving nickel sulfide chemical property is to form compound with basis material.
In document, the research work of representative nickel sulfide base electrode material comprises:
(1) the Yun Chan of KonKuk University of Korea S Kang professor research group adopts spray pyrolysis, with Ni (NO
3)
26H
2o is nickel source, and thiocarbamide is sulphur source, and sucrose is carbon source, has prepared NiS/C composite material.When wherein sucrose concentration is 0.1 mol/L, the chemical property of synthetic composite material is the most excellent.Under the current density of 1000 mA/g, circulate and still keep the reversible specific capacity of 472 mAh/g for 500 times, its capability retention is up to 86%(J. Power Sources, 2014,251,480-487).But this preparation process complex process, energy consumption is large, and cost is high.
(2) SanXia University's machinery is that Ni Shibing teaches research group using Ni net as reactant and supporter is prepared the NiS/Ni composite material with hollow structure with material, the electrode of preparing with this composite material, under the current density of 5C, specific capacity can reach 400 mAh/g, and can be under 0.15C current density stable circulation 100 times, capacitance loss rate is only 2.3%(J. Mater. Chem., 2012,22,2395-2397).But this preparation process technological parameter controllability is poor.
(3) Lang Leiming of Nanjing University professor research group is taking ethylenediamine as adjuvant, ethylene glycol is solvent, thioacetamide is sulphur source, the sea urchin shape nickel sulfide hollow ball that adopts simple solvent-thermal method to synthesize to be formed by nanometer rods, the electrode of preparing with this material, its first discharge capacity exceed 900 mAh/g, 10 times circulation after specific discharge capacity be about 350 mAh/g, 50 times circulation after specific discharge capacity still keep 200 mAh/g.But preparation process is used toxic organic compound ethylenediamine, have certain danger, and the capability retention of electrode is lower, and cyclical stability is poor.
Mainly concentrate on nanometer, Composite and design special appearance for the research of anode material of lithium battery NiS at present.Prepare compound and adopt spray pyrolysis, electrodeposition process more, but this type of preparation method's complex technical process, poor controllability, productive rate is low, and energy consumption is large, and cost is high.The NiS for preparing special appearance uses organic formwork or organic surface active agent mostly, and productive rate is low, and cost is high.The present invention is taking nickel salt as nickel source, and organic sulfur compound is sulphur source, prepares nano nickel sulphide by simple solvent-thermal method; Taking graphene oxide (GO) as carbon source, prepare nano nickel sulphide (NiS/graphene) composite material of Graphene encapsulation by electrostatic attraction method again.Because Graphene has high-specific surface area, high-flexibility, thereby can effectively alleviate the change in volume that active material produces in charge and discharge process, hinder the reunion of active material in charge and discharge process, suppress the dissolving of product in electrolyte, and ensure the structural stability of electrode in charge and discharge process.Meanwhile, the conductive network that graphene-based body forms can improve the electronic conductance of composite material, finally makes composite material show excellent cycle performance and high rate performance.Preparation is simple for this, output is large, be convenient to large-scale production.
Summary of the invention
The object of the present invention is to provide a kind of preparation method with lithium battery NiS/graphene composite positive pole Graphene encapsulating structure, that there is excellent electrochemical performance.
The preparation method who the invention provides a kind of lithium battery NiS/graphene composite positive pole, is characterized in that: nano nickel sulphide (NiS/graphene) composite material of preparing Graphene encapsulation by the method for electrostatic attraction.By dispersed graphene oxide (GO) matrix, GO surface band negative electrical charge, nanometer NiS, through the modification rear surface lotus that becomes positively charged, passes through the reduction of hydrazine hydrate under the effect of electrostatic attraction again, finally forms nano nickel sulphide (NiS/graphene) composite positive pole of Graphene encapsulation.This architectural feature takes full advantage of the advantage of Graphene high-specific surface area, high-flexibility, effectively alleviate the change in volume that nickel sulfide produces in charge and discharge process, and hinder the reunion of nickel sulfide in charge and discharge process, suppress the dissolving of product in electrolyte, make electrode structure in charge and discharge process, keep stable.
Its concrete steps are:
(1) configuration solution: the nickel salt of certain mol proportion and trisodium citrate are dissolved in a certain amount of solvent, and formation settled solution stirs.Wherein the concentration of nickel salt is controlled at 5 × 10
-4~ 2 × 10
-2mol/L, the concentration of trisodium citrate is controlled at 1 × 10
-3~ 4 × 10
-2mol/L, selecting organic sulfur compound is sulphur source, takes required quality, adds in above-mentioned solution, constantly stirs it is dissolved completely, wherein the concentration in sulphur source is controlled at 2 × 10
-4~ 1 × 10
-2mol/L.In solution, dropwise add ammoniacal liquor, and constantly stir the pH value of regulator solution;
(2) solution obtaining in step (1) is poured into in teflon-lined water heating kettle, in insulating box, under uniform temperature, reacted 12 ~ 48 h;
(3) by the product centrifugation obtaining in step (2), and with the washing of deionized water and ethanol, in the ultrasonic mixed liquor that is dispersed in deionized water and ethanol of powder obtaining the most at last, add a certain amount of surfactant to carry out surface modification to NiS, make positive charge on its surface band, this solution is labeled as solution A;
(4) by the ultrasonic mixed liquor that is scattered in deionized water and ethanol of the graphene oxide of certain mass (graphene oxide, GO), this solution is labeled as solution B;
(5) solution A in step (3) is slowly added in the solution B in step (4), add afterwards a certain amount of hydrazine hydrate and stir 1 ~ 3 h;
(6) product centrifugation step (5) being obtained, with deionized water and ethanol washing, in thermostatic drying chamber, dry at a certain temperature, by the NiS/graphene powder obtaining after dry in the tube furnace that is full of inert gas under uniform temperature heat treatment 1 ~ 3 h, to remove surperficial organic residue.
Wherein the described nickel salt of step (1) is nickel nitrate, nickel chloride, nickel acetate or its crystallization water compound.
The described solvent of step (1) is one or more in deionized water, absolute ethyl alcohol, methyl alcohol, ethylene glycol.
The described organic sulfur compound of step (1) can be one or more of ethyl mercaptan, propylene mercaptan, thiocarbamide, Cys.
In step (1), the pH of gained solution is adjusted to 8 ~ 13.
In step (2), the temperature of insulating box is 120 ~ 200
oc.
The described surfactant of step (3) can be one or more in 3-aminopropyl triethoxysilane (APTES), PDDA (PDDA), phenylamino methyl triethoxysilane, phenylamino methyltrimethoxy silane.
The uniform temperature that step (6) is described, refers to that heat treated temperature is 300 ~ 600
oc.
The present invention prepares nano nickel sulphide (NiS/graphene) composite material of Graphene encapsulation by the method for electrostatic attraction, dispersion and the encapsulation effect of Graphene to nickel sulfide can effectively cushion the volumetric expansion that nickel sulfide produces in charge and discharge process, suppress the dissolving of product in electrolyte in electrode process, thereby improve the cyclical stability of composite material.Meanwhile, Graphene provides good conductive network, is conducive to the fast transport of electronics, thereby has reduced electrode polarization, has improved greatly the high rate performance of composite material.The preparation technology who the invention has the advantages that nickel sulfide/grapheme composite positive electrode material is simple, and mild condition is applicable to large-scale industrial production.Nickel sulfide/graphene composite material prepared by the method has excellent chemical property, is a kind of desirable anode material of lithium battery, can be widely used in the fields such as various portable electric appts, electric automobile and Aero-Space.
Brief description of the drawings
Fig. 1 is the field emission scanning electron microscope picture of nickel sulfide/graphene composite material of embodiment 1.
Fig. 2 is the first charge-discharge curve chart of nickel sulfide/graphene composite material of embodiment 1.
Fig. 3 is the circulation volume figure of nickel sulfide/graphene composite material of embodiment 1.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but be not limited to protection scope of the present invention:
Embodiment 1:
Take 0.3 g Ni (CH
3cOO)
24H
2o, 0.5 g trisodium citrate is dissolved in 70 ml deionized waters, stir and form green settled solution, taking 0.2 g Cys adds in solution, stir and form brown color settled solution, in solution, add ammoniacal liquor, make the pH of solution be adjusted to 13, finally pour the red settled solution obtaining into 100 ml with in teflon-lined water heating kettle, 120
ounder C, react 12 h.The product centrifugation obtaining is also washed with deionized water and ethanol, in the ultrasonic mixed liquor that is dispersed in 40 ml deionized waters and 20 ml ethanol of powder obtaining the most at last, add 0.1 ml APTES to carry out surface modification to NiS, make positive charge on its surface band, this solution is labeled as solution A;
Take 10 mg graphene oxide (GO) powder, and by its ultrasonic mixed solution that is scattered in 70 ml deionized waters and 10 ml ethanol, this solution is labeled as solution B.Solution A is slowly added in solution B, and then adding 0.6 ml mass fraction is the hydrazine hydrate of 80 %, stirs 1 ~ 3 h.By the product centrifugation of gained, and with the washing of deionized water and ethanol, then in thermostatic drying chamber 70
ounder C, dry 8 h.Obtained powder is being full of to N
2in the tube furnace of gas 250
oc heat treatment 2 h, finally obtain nano nickel sulphide/graphene composite material.The 80 wt.% NiS/graphene composite materials, the acetylene black of 10 wt.% and the CMC of 10 wt.% that make are mixed, make slurry, be evenly coated on nickel screen, after vacuum drying, be stamped into circular electrode pole piece, taking lithium metal as to electrode, 1 mol/L LiPF
6/ EC+DEC+DMC(volume ratio is 1:1:1) be electrolyte, Celgard 2400 is barrier film, is assembled into button cell.Battery is carried out to constant current charge-discharge test, charging/discharging voltage scope is 0.01 ~ 3.0 V, result shows, it has good chemical property, under the current density of 0.1 A/g, reversible specific capacity is 1275 mAh/g first, and the specific capacity of material after 20 times that circulates is 817 mAh/g, and cyclical stability is good.
Embodiment 2:
Take 0.5 g Ni (CH
3cOO)
24H
2o, 0.5 g trisodium citrate is dissolved in 70 ml deionized waters, stir and form green settled solution, taking 0.5 g Cys adds in solution, stir and form brown color settled solution, in solution, add ammoniacal liquor, make the pH of solution be adjusted to 8 and stir 1 h, finally pour the red settled solution obtaining into 100 ml with in teflon-lined water heating kettle, 160
ounder C, react 20 h.The powder granule obtaining is separated and uses deionized water and ethanol washing, in the final ultrasonic mixed liquor that is dispersed in 50 ml deionized waters and 10 ml ethanol, add 0.6 ml APTES to carry out surface modification to NiS, make positive charge on its surface band, this solution is labeled as solution A;
Take 50 mg graphene oxide (GO) powder, and by its ultrasonic mixed solution that is scattered in 50 ml deionized waters and 50 ml ethanol, this solution is labeled as solution B.Solution A is slowly added in solution B, stir 1 h, then add the hydrazine hydrate that 1 ml mass fraction is 80%, stir 1 h and leave standstill one the whole night.By centrifugal the product of gained, and with the washing of deionized water and ethanol, then in thermostatic drying chamber 70
ounder C, dry 8 h.Obtained powder is being full of to N
2in the tube furnace of gas 300
oc heat treatment 2 h, finally obtain nano nickel sulphide/graphene composite material.The 80 wt.% NiS/graphene composite materials, the acetylene black of 10 wt.% and the CMC of 10 wt.% that make are mixed, make slurry, be evenly coated on nickel screen, after vacuum drying, be stamped into circular electrode pole piece, taking lithium metal as to electrode, 1 mol/L LiPF
6/ EC+DEC+DMC(volume ratio is 1:1:1) be electrolyte, Celgard 2400 is barrier film, is assembled into button cell.Battery is carried out to constant current charge-discharge test, charging/discharging voltage scope is 0.01 ~ 3.0 V, result shows, it has good chemical property, under the current density of 0.1 A/g, reversible specific capacity is 1275 mAh/g first, and the specific capacity of material after 20 times that circulates is 817 mAh/g, and cyclical stability is good.
Embodiment 3:
Take 0.4 g Ni (CH
3cOO)
24H
2o, 0.5 g trisodium citrate is dissolved in 70 ml deionized waters, stir and form green settled solution, taking 0.9 g Cys adds in solution, stir and form brown color settled solution, in solution, add ammoniacal liquor, make the pH of solution be adjusted to 10 and stir 1 h, finally pour the red settled solution obtaining into 100 ml with in teflon-lined water heating kettle, 180
ounder C, react 36 h.The powder granule obtaining is separated and uses deionized water and ethanol washing, in the final ultrasonic mixed liquor that is dispersed in 40 ml deionized waters and 20 ml ethanol, add 0.1 ml APTES to carry out surface modification to NiS, make positive charge on its surface band, this solution is labeled as solution A;
Take 30 mg graphene oxide (GO) powder, and by its ultrasonic mixed solution that is scattered in 30 ml deionized waters and 50 ml ethanol, this solution is labeled as solution B.Solution A is slowly added in solution B, stir 1 h, then add the hydrazine hydrate that 1.6 ml mass fractions are 80%, stir 1 h and leave standstill one the whole night.By centrifugal the product of gained, and with the washing of deionized water and ethanol, then in thermostatic drying chamber 70
ounder C, dry 8 h.Obtained powder is being full of to N
2in the tube furnace of gas 350
oc heat treatment 2 h, finally obtain nano nickel sulphide/graphene composite material.The 80 wt.% NiS/graphene composite materials, the acetylene black of 10 wt.% and the CMC of 10 wt.% that make are mixed, make slurry, be evenly coated on nickel screen, after vacuum drying, be stamped into circular electrode pole piece, taking lithium metal as to electrode, 1 mol/L LiPF
6/ EC+DEC+DMC(volume ratio is 1:1:1) be electrolyte, Celgard 2400 is barrier film, is assembled into button cell.Battery is carried out to constant current charge-discharge test, charging/discharging voltage scope is 0.01 ~ 3.0 V, result shows, it has good chemical property, under the current density of 0.1 A/g, reversible specific capacity is 1275 mAh/g first, and the specific capacity of material after 20 times that circulates is 817 mAh/g, and cyclical stability is good.
Claims (7)
1. nano nickel sulphide/grapheme composite positive electrode material and preparation method thereof, it is characterized in that adopting the nickel sulfide that solvent-thermal method is prepared to there is nanoscale and uniform particles, by electrostatic attraction effect, synthesize the nano nickel sulphide/grapheme composite positive electrode material with encapsulating structure, concrete technology step is:
(1) configuration solution: the nickel salt of certain mol proportion and trisodium citrate are dissolved in a certain amount of solvent, and formation settled solution stirs; Take a certain amount of organic sulfur source and join in above-mentioned solution, constantly stir it is dissolved completely; In solution, dropwise add afterwards ammoniacal liquor, and constantly stir, the pH value of regulator solution is adjusted to 8 ~ 13; Wherein the concentration of nickel salt is controlled at 5 × 10
-4~ 2 × 10
-2mol/L, the concentration of trisodium citrate is controlled at 1 × 10
-3~ 4 × 10
-2mol/L, the concentration in sulphur source is controlled at 2 × 10
-4~ 1 × 10
-2mol/L;
(2) solution obtaining in step (1) is poured into in teflon-lined water heating kettle, in insulating box, under uniform temperature, reacted 12 ~ 48 h;
(3) by the product centrifugation obtaining in step (2), and wash repeatedly with deionized water and ethanol, in the ultrasonic mixed liquor that is dispersed in deionized water and ethanol of powder obtaining the most at last, add a certain amount of surfactant to carry out surface modification to NiS, make positive charge on its surface band, this solution is labeled as solution A;
(4) by ultrasonic the graphene oxide of the certain mass mixed liquor that is scattered in deionized water and ethanol, this solution is labeled as solution B;
(5) solution A in step (3) is slowly added in the solution B in step (4), add afterwards a certain amount of hydrazine hydrate and stir 1 ~ 3 h;
(6) product centrifugation step (5) being obtained with the washing of deionized water and ethanol, is dried in thermostatic drying chamber, by the NiS/graphene powder obtaining after dry in the tube furnace that is full of inert gas under uniform temperature heat treatment 1 ~ 3 h.
2. nano nickel sulphide/grapheme composite positive electrode material according to claim 1 and preparation method thereof, is characterized in that: the described nickel salt of step (1) is nickel nitrate, nickel chloride, nickel acetate or its crystallization water compound.
3. nano nickel sulphide/grapheme composite positive electrode material according to claim 1 and preparation method thereof, is characterized in that: the described solvent of step (1) is one or more in deionized water, absolute ethyl alcohol, methyl alcohol, ethylene glycol.
4. nano nickel sulphide/grapheme composite positive electrode material according to claim 1 and preparation method thereof, is characterized in that: the described organic sulfur compound of step (1) is one or more of ethyl mercaptan, propylene mercaptan, thiocarbamide, Cys.
5. nano nickel sulphide/grapheme composite positive electrode material according to claim 1 and preparation method thereof, is characterized in that: in step (2), the temperature of insulating box is 120 ~ 200
oc.
6. nano nickel sulphide/grapheme composite positive electrode material according to claim 1 and preparation method thereof, is characterized in that: the described surfactant of step (3) is one or more in 3-aminopropyl triethoxysilane, PDDA, phenylamino methyl triethoxysilane, phenylamino methyltrimethoxy silane.
7. nano nickel sulphide/grapheme composite positive electrode material according to claim 1 and preparation method thereof, is characterized in that: the uniform temperature that step (6) is described, refers to that heat treated temperature is 300 ~ 600
oc.
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