CN106410199A - Preparation method of graphene/ferro-tin alloy composite anode material for lithium ion battery - Google Patents
Preparation method of graphene/ferro-tin alloy composite anode material for lithium ion battery Download PDFInfo
- Publication number
- CN106410199A CN106410199A CN201610831531.4A CN201610831531A CN106410199A CN 106410199 A CN106410199 A CN 106410199A CN 201610831531 A CN201610831531 A CN 201610831531A CN 106410199 A CN106410199 A CN 106410199A
- Authority
- CN
- China
- Prior art keywords
- graphene
- ferro
- preparation
- tin alloy
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
-
- 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 belongs to the field of preparation of a composite material, and relates to a preparation method of a graphene/ferro-tin alloy composite anode material for a lithium ion battery. The preparation method comprises the main steps of: using natural flake graphite as a raw material, after obtaining graphite oxide, carrying out ultrasonic dispersion on the graphite oxide in water and alcohol mixed solution, then adding SnC14.5H2O and K3[Fe(CN)6] solution, and performing a hydrothermal reaction for 24 h at a temperature of 80 to 150 DEG C; and after cooling, collecting precipitates, and washing and drying the precipitates to obtain a graphene oxide/Sn3[Fe(CN)6]4 precursor, then calcining the precursor in an inert atmosphere to obtain the graphene/ferro-tin alloy nano composite material (FeSn2@Sn/rGO). FeSn2@Sn nano particles in the graphene/ferro-tin alloy composite anode material disclosed by the invention are tightly attached to the surface of graphene, and are uniformly dispersed; and when the graphene/ferro-tin alloy composite anode material is used as a lithium ion battery anode material, under a current density of 200mA g-1, first discharge specific capacity reaches 1,598 mAh g-1, and after circulation is carried out for 60 times, the capacity reaches 970 mA h g-1. The preparation method disclosed by the invention is simple and easy to operate in operation process, short in reaction time and easy for industrial implementation.
Description
Technical field
The invention belongs to field of composite material preparation, multiple particularly to a kind of lithium ion battery Graphene/ferro-tin alloy
Close the preparation method of negative material.
Technical background
With the expanding day of demand for energy, people start to be devoted to grinding of high efficiency high-energy-density energy storage device
Study carefully.Lithium ion battery is high due to energy density, low-maintenance cost, and self-discharge current is little, has become as most popular chargeable electricity
Pond, is widely used in various electronic equipments and electric automobile.Traditional lithium ion battery negative material is graphite, hard carbon, soft
The material with carbon elements such as carbon.As a kind of emerging carbon family member, Graphene has many extremely excellent performances, as high current-carrying
Transport factor, great specific surface area, excellent heat conductivility, good translucency, high chemically and thermally stability etc., make stone
Black alkene is once it is found that cause the research boom of new round material with carbon element.In alternative negative material, the theoretical appearance of metallic tin
Amount is up to 990 mAh g-1, and friendly with electrolyte, thus paid close attention to by people.But it also cannot avoid metal material simultaneously
Common fault in lithium ion battery charge and discharge process：During lithium ion inserts embedding deintercalation, the Volume Changes of electrode material are larger, and one
As reach three times of raw material, thus causing the serious efflorescence of electrode material even to pulverize, greatly reduce the stability of structure,
Reduce cycle performance, have a strong impact on the performance of electrode material.Numerous studies show that the composite material exhibits of nanostructured go out more
Excellent chemical property.The Graphene having excellent properties is combined with tin-based material, and it is multiple to prepare graphene-based ferro-tin alloy
Close negative material, be the effective way preparing high performance lithium ionic cell cathode material.On the one hand, the ferro-tin alloy of load in situ
Nano-particle can expand Graphene lamella distance in the solid state, prevents it to be piled into graphite-structure, thus keeping Graphene
Superior function.On the other hand, there is cooperative effect, the tin of nanostructured in addition between Graphene and ferro-tin alloy nano-particle
Based alloy and the iron that adds as inert metal can effectively buffer electrode material huge in the embedded of lithium ion and during deviating from
Large volume expands the structure collapses causing and because the capacity that structure collapses cause is decayed so that composite material exhibits go out ratio rapidly
The more superior chemical property of one pack system, or even produce some new characteristics.Before the present invention utilizes metallic organic framework first
Drive body method, prepare graphene-based ferro-tin alloy composite, this composite is as lithium ion battery negative material, table
Reveal higher specific capacity（970 mAh g-1）With excellent cyclical stability.
Content of the invention
The present invention already allows for produced problem in prior art, adopts the metallic organic framework (Sn of iron content, tin3
[Fe(CN)6]4) be supported in situ on the graphene film of sheet, then thermal decomposition presoma is prepared on Graphene in an inert atmosphere
The compound of load ferro-tin alloy nano-particle.Not only method is novel simply for the method, composite effect is good, and controllable product
Pattern and micro-structural.
Present invention aim at providing a kind of system of lithium ion battery Graphene/ferro-tin alloy nano composition
Preparation Method, comprises the steps：
（1) with natural flake graphite as raw material, it is oxidized with Hummers method and obtains graphite oxide；
（2）The preparation of solution a：By step（1）Prepared graphite oxide ultrasonic disperse, in alcohol-water mixture, obtains graphite oxide
Alkene dispersion liquid；
（3）The preparation of solution b：Tetravalence pink salt is dissolved in dilute hydrochloric acid solution, adds a certain amount of block copolymer surface to live
Property agent；
（4）The preparation of solution c：The potassium ferricyanide is dissolved in dilute hydrochloric acid solution；
（5）Solution b is added in solution a, is stirred at room temperature, form mixed solution, solution c is added to mixed solution
In, continue stirring, the mixed solution of final gained is added in teflon-lined reactor, then reactor is put
Carry out hydro-thermal reaction in baking oven, by gained precipitation and centrifugal separation, deionized water is washed, and is dried, obtains Sn3[Fe(CN)6]4/
RGO precursor；
（6）By step（5）Temperature programming, to calcining heat, after calcining, obtains Graphene to the presoma of gained in an inert atmosphere
Upper load ferro-tin alloy composite negative pole material, i.e. Graphene/ferro-tin alloy composite negative pole material.
Step（2）In, described alcohol-water mixture is mixed liquor or deionized water and the ethanol of deionized water and ethylene glycol
Mixed liquor, in described graphene oxide dispersion the concentration of graphite oxide be 1-5 mg/mL.
Step（3）In tetravalence pink salt used be SnCl4·5H2O, concentration is 10-30 mg/mL, described block copolymer
Surfactant is polyethers F127.
Step（4）Described in potassium ferricyanide solution concentration be 10-50 mg/mL.
Step（5）Described in graphite oxide in mixed solution：Tetravalence pink salt：The mass ratio of the potassium ferricyanide is 17:80:
100-68:80:100, hydrothermal temperature is 80-150 DEG C, and the reaction time is 10-24 h.
Step（6）Middle inert gas is nitrogen or argon gas, and heating rate is 2-5 DEG C/min, and calcining heat is 600-800
DEG C, calcination time is 1-3 h.
In products therefrom of the present invention, ferro-tin alloy nano-particle is closely attached to the surface of redox graphene, and iron
Tin alloy nano-particle is cube block structure, and the length of side is 50-150 nm.
Beneficial effects of the present invention：
This method operating procedure is simple, and the reaction time is short, and Environmental Safety, and low cost, can be potential it is easy to industrializing implementation
Apply in lithium ion battery negative material.
Brief description
Fig. 1 is that the X-ray of the redox graphene/ferro-tin alloy nano composite material of the embodiment of the present invention 1 preparation is spread out
Penetrate（XRD）Collection of illustrative plates, wherein abscissa are the angle of diffraction（2θ）, unit is degree（°）, ordinate is diffracted intensity, and unit is cps.
Fig. 2 is the transmission electron microscope of the redox graphene/ferro-tin alloy nano composite material of the embodiment of the present invention 1 preparation
（TEM）Photo.
Fig. 3 is that the redox graphene/ferro-tin alloy nano composite material of the embodiment of the present invention 1 preparation is used as lithium ion
Cell negative electrode material is 200 mA g in current density-1Under cycle performance figure.
Specific embodiment：
With specific embodiment, technical scheme is described in detail below in conjunction with the accompanying drawings, but protection scope of the present invention
It is not limited to these embodiments.
Embodiment 1：
By 80 mg graphite oxide ultrasonic disperse in 10 ml water and 14 ml ethylene glycol mixtures, ultrasonic 2 h obtain graphite oxide
Alkene dispersion liquid.Add 8 mlSnCl4·5H2The HCl solution of O and F127（Containing SnCl4·5H2O 140 mg, F127 150 mg,
HCl concentration is 0.01 mol/L）, after stirring at normal temperature 30 min, add 8 mlK3[Fe(CN)6] solution（Containing K3[Fe(CN)6]
175.6 mg, HCl concentration is 0.01 mol/L）, stirring at normal temperature 30 min, mixed liquor is added in 50 ml polytetrafluoroethylene (PTFE)
In the reactor of lining, in baking oven, 120 DEG C of hydro-thermal reaction 24 h, product is centrifuged, and deionized water/absolute ethanol washing obtains
Obtain cube block Sn of load on Graphene3[Fe(CN)6]4Nanoparticle precursor, product is vacuum dried at 45 DEG C.
Presoma is positioned in porcelain boat in N2Calcine at 700 DEG C in the tube furnace of protection, heating rate is 5 DEG C/min, calcination time
For 1 h, obtain final product redox graphene/ferro-tin alloy nano composite material（FeSn2@Sn/rGO）.
Fig. 1 is the XRD of the product of the embodiment of the present invention 1 preparation, in addition to the diffraction maximum of redox graphene, other
Peak corresponds to FeSn2And Sn, redox graphene/ferro-tin alloy nano composite material is described（FeSn2@Sn/rGO）Successfully made
For out.
Fig. 2 is that the TEM of the product of the embodiment of the present invention 1 preparation schemes it can be seen that ferro-tin alloy nano cubic block is uniform
It is attached to the surface of redox graphene piece, the wherein ferro-tin alloy nano-particle length of side is 50-150 nm.
Fig. 3 is the redox graphene/ferro-tin alloy nano composite material of the embodiment of the present invention 1 preparation as lithium ion
Cell negative electrode material is 200 mA g in current density-1When cycle performance figure.
Embodiment 2：
By 80 mg graphite oxide ultrasonic disperse in 10 ml water and 14 ml ethylene glycol mixtures.Add 8 ml SnCl4·
5H2The HCl solution of O and F127（Containing SnCl4·5H2O 140 mg, F127 150 mg, HCl concentration is 0.01 mol/L）, normal temperature
Stir 30 min.It is subsequently adding 8 ml K3[Fe(CN)6] solution（Containing K3[Fe(CN)6] 175.6 mg, HCl concentration is 0.01
mol/L）, stirring at normal temperature 30 min, add 50 ml teflon-lined reactor 100 DEG C of hydro-thermal reactions 24 in baking oven
h.After natural cooling, by sample centrifugation, deionized water and absolute ethanol washing respectively, by product, at 45 DEG C, vacuum is done
Dry.The product obtaining is positioned in porcelain boat, in N2Protection tube furnace in 700 DEG C calcining 1 h, heating rate be 5 DEG C/
Min, obtains final product.
Embodiment 3：
By 70 mg graphite oxide ultrasonic disperse in 10 ml water and 14 ml alcohol mixeding liquids.Add 8 ml SnCl4·5H2O
HCl solution with F127（Containing SnCl4·5H2O 140 mg, F127 150 mg, HCl concentration is 0.01 mol/L）, stirring at normal temperature
30 min.It is subsequently adding 8 ml K3[Fe(CN)6] solution（Containing K3[Fe(CN)6] 175.6 mg, HCl concentration is 0.01 mol/
L）, stirring at normal temperature 30 min, add 50 ml teflon-lined reactors, 120 DEG C of hydro-thermal reaction 24 h in baking oven.From
After so cooling down, by sample centrifugation, deionized water and absolute ethanol washing, product is vacuum dried at 45 DEG C respectively.
The product obtaining is positioned in porcelain boat, in N2700 DEG C of calcining 1 h in the tube furnace of protection, heating rate is 5 DEG C/min, obtains
To final product.
Embodiment 4：
By 70 mg graphite oxide ultrasonic disperse in 10 ml water and 14 ml alcohol mixeding liquids.Add 8 ml SnCl4·5H2O
HCl solution with F127（Containing SnCl4·5H2O140 mg, F127 150 mg, HCl concentration is 0.01 mol/L）, stirring at normal temperature
30 min.It is subsequently adding 8 ml K3[Fe(CN)6] solution（Containing K3[Fe(CN)6] 175.6 mg, HCl concentration is 0.01 mol/
L）, stirring at normal temperature 30 min, add 50 ml teflon-lined reactors, 150 DEG C of hydro-thermal reaction 24 h in baking oven.From
After so cooling down, by sample centrifugation, deionized water and absolute ethanol washing, product is vacuum dried at 45 DEG C respectively.
The product obtaining is positioned in porcelain boat, in N2700 DEG C of calcining 1 h in the tube furnace of protection, heating rate is 5 DEG C/min, obtains
To final product.
Embodiment 5：
By 70 mg graphite oxide ultrasonic disperse in 10 ml water and 14 ml ethylene glycol mixtures.Add 8 ml SnCl4·
5H2The HCl solution of O and F127（Containing SnCl4·5H2O 140 mg, F127 150 mg, HCl concentration is 0.01 mol/L）, normal temperature
Stir 30 min.It is subsequently adding 8 ml K3[Fe(CN)6] solution（Containing K3[Fe(CN)6] 175.6 mg, HCl concentration is 0.01
mol/L）, stirring at normal temperature 30 min, add 50 ml teflon-lined reactor 100 DEG C of hydro-thermal reactions 24 in baking oven
h.After natural cooling, by sample centrifugation, deionized water and absolute ethanol washing respectively, by product, at 45 DEG C, vacuum is done
Dry.The product obtaining is positioned in porcelain boat, in N2Protection tube furnace in 600 DEG C calcining 1 h, heating rate be 5 DEG C/
Min, obtains final product.
Embodiment 6：
By 70 mg graphite oxide ultrasonic disperse in 10 ml water and 14 ml ethylene glycol mixtures.Add 8 ml SnCl4·
5H2The HCl solution of O and F127（Containing SnCl4·5H2O 140 mg, F127 150 mg, HCl concentration is 0.01 mol/L）, normal temperature
Stir 30 min.It is subsequently adding 8 ml K3[Fe(CN)6] solution（Containing K3[Fe(CN)6] 175.6 mg, HCl concentration is 0.01
mol/L）, stirring at normal temperature 30 min, add 50 ml teflon-lined reactor 100 DEG C of hydro-thermal reactions 24 in baking oven
h.After natural cooling, by sample centrifugation, deionized water and absolute ethanol washing respectively, by product, at 45 DEG C, vacuum is done
Dry.The product obtaining is positioned in porcelain boat, in N2Protection tube furnace in 800 DEG C calcining 1 h, heating rate be 5 DEG C/
Min, obtains final product.
Embodiment 7：
By 90 mg graphite oxide ultrasonic disperse in 10 ml water and 14 ml ethylene glycol mixtures.Add 8 ml SnCl4·
5H2The HCl solution of O and F127（Containing SnCl4·5H2O 140 mg, F127 150 mg, HCl concentration is 0.01 mol/L）, normal temperature
Stir 30 min.It is subsequently adding 8 ml K3[Fe(CN)6] solution（Containing K3[Fe(CN)6] 175.6 mg, HCl concentration is 0.01
mol/L）, stirring at normal temperature 30 min, add 50 ml teflon-lined reactor 100 DEG C of hydro-thermal reactions 24 in baking oven
h.After natural cooling, by sample centrifugation, deionized water and absolute ethanol washing respectively, by product, at 45 DEG C, vacuum is done
Dry.The product obtaining is positioned in porcelain boat, in N2Protection tube furnace in 700 DEG C calcining 1 h, heating rate be 2 DEG C/
Min, obtains final product.
Embodiment 8：
By 90 mg graphite oxide ultrasonic disperse in 10 ml water and 14 ml ethylene glycol mixtures.Add 8 ml SnCl4·
5H2The HCl solution of O and F127（Containing SnCl4·5H2O 140 mg, F127 150 mg, HCl concentration is 0.01 mol/L）, normal temperature
Stir 30 min.It is subsequently adding 8 ml K3[Fe(CN)6] solution（Containing K3[Fe(CN)6] 175.6 mg, HCl concentration is 0.01
mol/L）, stirring at normal temperature 30 min, add 50 ml teflon-lined reactor 100 DEG C of hydro-thermal reactions 24 in baking oven
h.After natural cooling, by sample centrifugation, deionized water and absolute ethanol washing respectively, by product, at 45 DEG C, vacuum is done
Dry.The product obtaining is positioned in porcelain boat, in N2Protection tube furnace in 600 DEG C calcining 1 h, heating rate be 2 DEG C/
Min, obtains final product.
Embodiment 9：
By 70 mg graphite oxide ultrasonic disperse in 10 ml water and 14 ml ethylene glycol mixtures.Add 8 ml SnCl4·
5H2The HCl solution of O and F127（Containing SnCl4·5H2O 140 mg, F127 150 mg, HCl concentration is 0.01 mol/L）, normal temperature
Stir 30 min.It is subsequently adding 8 ml K3[Fe(CN)6] solution（Containing K3[Fe(CN)6] 175.6 mg, HCl concentration is 0.01
mol/L）, stirring at normal temperature 30 min, add 50 ml teflon-lined reactor 100 DEG C of hydro-thermal reactions 24 in baking oven
h.After natural cooling, by sample centrifugation, deionized water and absolute ethanol washing respectively, by product, at 45 DEG C, vacuum is done
Dry.The product obtaining is positioned in porcelain boat, in N2Protection tube furnace in 800 DEG C calcining 1 h, heating rate be 2 DEG C/
Min, obtains final product.
Embodiment 10：
By 30 mg graphite oxide ultrasonic disperse in 10 ml water and 14 ml ethylene glycol mixtures.Add 8 ml SnCl4·
5H2The HCl solution of O and F127（Containing SnCl4·5H2O 140 mg, F127 150 mg, HCl concentration is 0.01 mol/L）, normal temperature
Stir 30 min.It is subsequently adding 8 ml K3[Fe(CN)6] solution（Containing K3[Fe(CN)6] 175.6 mg, HCl concentration is 0.01
mol/L）, stirring at normal temperature 30 min, add 50 ml teflon-lined reactor 100 DEG C of hydro-thermal reactions 24 in baking oven
h.After natural cooling, by sample centrifugation, deionized water and absolute ethanol washing respectively, by product, at 45 DEG C, vacuum is done
Dry.The product obtaining is positioned in porcelain boat, in N2Protection tube furnace in 700 DEG C calcining 1 h, heating rate be 5 DEG C/
Min, obtains final product.
Embodiment 11：
By 50 mg graphite oxide ultrasonic disperse in 10 ml water and 14 ml ethylene glycol mixtures.Add 8 ml SnCl4·
5H2The HCl solution of O and F127（Containing SnCl4·5H2O 140 mg, F127 150 mg, HCl concentration is 0.01 mol/L）, normal temperature
Stir 30 min.It is subsequently adding 8 ml K3[Fe(CN)6] solution（Containing K3[Fe(CN)6] 175.6 mg, HCl concentration is 0.01
mol/L）, stirring at normal temperature 30 min, add 50 ml teflon-lined reactor 120 DEG C of hydro-thermal reactions 24 in baking oven
h.After natural cooling, by sample centrifugation, deionized water and absolute ethanol washing respectively, by product, at 45 DEG C, vacuum is done
Dry.The product obtaining is positioned in porcelain boat, in N2Protection tube furnace in 700 DEG C calcining 1 h, heating rate be 5 DEG C/
Min, obtains final product.
Embodiment 12：
By 50 mg graphite oxide ultrasonic disperse in 10 ml water and 14 ml ethylene glycol mixtures.Add 8 ml SnCl4·
5H2The HCl solution of O and F127（Containing SnCl4·5H2O 140 mg, F127 150 mg, HCl concentration is 0.01 mol/L）, normal temperature
Stir 30 min.It is subsequently adding 8 ml K3[Fe(CN)6] solution（Containing K3[Fe(CN)6] 175.6 mg, HCl concentration is 0.01
mol/L）, stirring at normal temperature 30 min, add 50 ml teflon-lined reactor 150 DEG C of hydro-thermal reactions 24 in baking oven
h.After natural cooling, by sample centrifugation, deionized water and absolute ethanol washing respectively, by product, at 45 DEG C, vacuum is done
Dry.The product obtaining is positioned in porcelain boat, in N2Protection tube furnace in 700 DEG C calcining 1 h, heating rate be 5 DEG C/
Min, obtains final product.
Embodiment 13：
By 50 mg graphite oxide ultrasonic disperse in 10 ml water and 14 ml ethylene glycol mixtures.Add 8 ml SnCl4·
5H2The HCl solution of O and F127（Containing SnCl4·5H2O 140 mg, F127 150 mg, HCl concentration is 0.01 mol/L）, normal temperature
Stir 30 min.It is subsequently adding 8 ml K3[Fe(CN)6] solution（Containing K3[Fe(CN)6] 175.6 mg, HCl concentration is 0.01
mol/L）, stirring at normal temperature 30 min, add 50 ml teflon-lined reactor 100 DEG C of hydro-thermal reactions 24 in baking oven
h.After natural cooling, by sample centrifugation, deionized water and absolute ethanol washing respectively, by product, at 45 DEG C, vacuum is done
Dry.The product obtaining is positioned in porcelain boat, in N2Protection tube furnace in 600 DEG C calcining 1 h, heating rate be 2 DEG C/
Min, obtains final product.
Embodiment 14：
By 100 mg graphite oxide ultrasonic disperse in 10 ml water and 14 ml ethylene glycol mixtures.Add 8 ml SnCl4·
5H2The HCl solution of O and F127（Containing SnCl4·5H2O 140 mg, F127 150 mg, HCl concentration is 0.01 mol/L）, normal temperature
Stir 30 min.It is subsequently adding 8 ml K3[Fe(CN)6] solution（Containing K3[Fe(CN)6] 175.6 mg, HCl concentration is 0.01
mol/L）, stirring at normal temperature 30 min, add 50 ml teflon-lined reactor 100 DEG C of hydro-thermal reactions 24 in baking oven
h.After natural cooling, by sample centrifugation, deionized water and absolute ethanol washing respectively, by product, at 45 DEG C, vacuum is done
Dry.The product obtaining is positioned in porcelain boat, in N2Protection tube furnace in 700 DEG C calcining 1 h, heating rate be 5 DEG C/
Min, obtains final product.
Embodiment 15：
By 100 mg graphite oxide ultrasonic disperse in 10 ml water and 14 ml ethylene glycol mixtures.Add 8 ml SnCl4·
5H2The HCl solution of O and F127（Containing SnCl4·5H2O 140 mg, F127 150 mg, HCl concentration is 0.01 mol/L）, normal temperature
Stir 30 min.It is subsequently adding 8 ml K3[Fe(CN)6] solution（Containing K3[Fe(CN)6] 175.6 mg, HCl concentration is 0.01
mol/L）, stirring at normal temperature 30 min, add 50 ml teflon-lined reactor 120 DEG C of hydro-thermal reactions 24 in baking oven
h.After natural cooling, by sample centrifugation, deionized water and absolute ethanol washing respectively, by product, at 45 DEG C, vacuum is done
Dry.The product obtaining is positioned in porcelain boat, in N2Protection tube furnace in 600 DEG C calcining 1 h, heating rate be 5 DEG C/
Min, obtains final product.
Embodiment 16：
By 100 mg graphite oxide ultrasonic disperse in 10 ml water and 14 ml ethylene glycol mixtures.Add 8 ml SnCl4·
5H2The HCl solution of O and F127（Containing SnCl4·5H2O 140 mg, F127 150 mg, HCl concentration is 0.01 mol/L）, normal temperature
Stir 30 min.It is subsequently adding 8 ml K3[Fe(CN)6] solution（Containing K3[Fe(CN)6] 175.6 mg, HCl concentration is 0.01
mol/L）, stirring at normal temperature 30 min, add 50 ml teflon-lined reactor 150 DEG C of hydro-thermal reactions 24 in baking oven
h.After natural cooling, by sample centrifugation, deionized water and absolute ethanol washing respectively, by product, at 45 DEG C, vacuum is done
Dry.The product obtaining is positioned in porcelain boat, in N2Protection tube furnace in 800 DEG C calcining 1 h, heating rate be 5 DEG C/
Min, obtains final product.
Embodiment 17：
By 120 mg graphite oxide ultrasonic disperse in 10 ml water and 14 ml ethylene glycol mixtures.Add 8 ml SnCl4·
5H2The HCl solution of O and F127（Containing SnCl4·5H2O 140 mg, F127 150 mg, HCl concentration is 0.01 mol/L）, normal temperature
Stir 30 min.It is subsequently adding 8 ml K3[Fe(CN)6] solution（Containing K3[Fe(CN)6] 175.6 mg, HCl concentration is 0.01
mol/L）, stirring at normal temperature 30 min, add 50 ml teflon-lined reactor 150 DEG C of hydro-thermal reactions 24 in baking oven
h.After natural cooling, by sample centrifugation, deionized water and absolute ethanol washing respectively, by product, at 45 DEG C, vacuum is done
Dry.The product obtaining is positioned in porcelain boat, in N2800 DEG C of calcining 1 h in the tube furnace of protection, heating rate is 5 DEG C/min,
Obtain final product.
Claims (6)
1. a kind of preparation method of lithium ion battery Graphene/ferro-tin alloy composite negative pole material it is characterised in that include with
Lower step：
（1) with natural flake graphite as raw material, it is oxidized with Hummers method and obtains graphite oxide；
（2）The preparation of solution a：By step（1）Prepared graphite oxide ultrasonic disperse, in alcohol-water mixture, obtains graphite oxide
Alkene dispersion liquid；
（3）The preparation of solution b：Tetravalence pink salt is dissolved in dilute hydrochloric acid solution, adds a certain amount of block copolymer surface to live
Property agent；
（4）The preparation of solution c：The potassium ferricyanide is dissolved in dilute hydrochloric acid solution；
（5）Solution b is added in solution a, is stirred at room temperature, form mixed solution, solution c is added to mixed solution
In, continue stirring, the mixed solution of final gained is added in teflon-lined reactor, then reactor is put
Carry out hydro-thermal reaction in baking oven, by gained precipitation and centrifugal separation, deionized water is washed, and is dried, obtains Sn3[Fe(CN)6]4/
RGO precursor；
（6）By step（5）Temperature programming, to calcining heat, after calcining, obtains Graphene to the presoma of gained in an inert atmosphere
Upper load ferro-tin alloy composite negative pole material, i.e. Graphene/ferro-tin alloy composite negative pole material.
2. the preparation method of a kind of lithium ion battery Graphene/ferro-tin alloy composite negative pole material according to claim 1,
It is characterized in that：Step（2）In, described alcohol-water mixture is mixed liquor or deionized water and the second of deionized water and ethylene glycol
The mixed liquor of alcohol, in described graphene oxide dispersion, the concentration of graphite oxide is 1-5 mg/mL.
3. the preparation method of a kind of lithium ion battery Graphene/ferro-tin alloy composite negative pole material according to claim 1,
It is characterized in that：Step（3）In tetravalence pink salt used be SnCl4·5H2O, concentration is 10-30 mg/mL, described block copolymerization
Thing surfactant is polyethers F127.
4. the preparation method of a kind of lithium ion battery Graphene/ferro-tin alloy composite negative pole material according to claim 1,
It is characterized in that, step（4）Described in potassium ferricyanide solution concentration be 10-50 mg/mL.
5. the preparation method of a kind of lithium ion battery Graphene/ferro-tin alloy composite negative pole material according to claim 1,
It is characterized in that, step（5）Described in graphite oxide in mixed solution：Tetravalence pink salt：The mass ratio of the potassium ferricyanide is 17:
80:100-68:80:100, hydrothermal temperature is 80-150 DEG C, and the reaction time is 10-24 h.
6. the preparation method of a kind of lithium ion battery Graphene/ferro-tin alloy composite negative pole material according to claim 1,
It is characterized in that, step（6）Middle inert gas is nitrogen or argon gas, and heating rate is 2-5 DEG C/min, and calcining heat is 600-
800 DEG C, calcination time is 1-3 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610831531.4A CN106410199B (en) | 2016-09-20 | 2016-09-20 | A kind of lithium ion battery graphene/ferro-tin alloy composite negative pole material preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610831531.4A CN106410199B (en) | 2016-09-20 | 2016-09-20 | A kind of lithium ion battery graphene/ferro-tin alloy composite negative pole material preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106410199A true CN106410199A (en) | 2017-02-15 |
| CN106410199B CN106410199B (en) | 2018-12-14 |
Family
ID=57996687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610831531.4A Active CN106410199B (en) | 2016-09-20 | 2016-09-20 | A kind of lithium ion battery graphene/ferro-tin alloy composite negative pole material preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106410199B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107195884A (en) * | 2017-06-01 | 2017-09-22 | 河南理工大学 | A kind of lithium metasilicate doped graphene lithium ion battery negative material and preparation method thereof |
| CN107799748A (en) * | 2017-10-23 | 2018-03-13 | 天津师范大学 | A kind of nanoscale cube cobaltous stannate and graphene composite material and preparation method and application |
| CN108554434A (en) * | 2018-04-16 | 2018-09-21 | 复旦大学 | Metal@graphitized carbons/graphene complex electrocatalyst materials and preparation method thereof |
| CN108597895A (en) * | 2018-06-05 | 2018-09-28 | 哈尔滨工程大学 | A kind of bimetallic oxide and graphene composite material and preparation method thereof |
| CN112331815A (en) * | 2020-11-04 | 2021-02-05 | 四川大学 | Three-dimensional micro-nano composite porous iron-tin-iron-tin nitrogen compound integrated lithium ion battery cathode and one-step preparation method thereof |
| CN114141992A (en) * | 2021-11-30 | 2022-03-04 | 四川启睿克科技有限公司 | Self-propagating alloyed lithium negative electrode and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102800849A (en) * | 2012-07-23 | 2012-11-28 | 浙江大学 | Transition metal tin compound/graphene composite material and preparation method and application thereof |
| CN103290246A (en) * | 2013-05-27 | 2013-09-11 | 南京师范大学 | Preparation method of three-dimensional nano porous tin-base alloy for lithium-ion battery negative electrode |
-
2016
- 2016-09-20 CN CN201610831531.4A patent/CN106410199B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102800849A (en) * | 2012-07-23 | 2012-11-28 | 浙江大学 | Transition metal tin compound/graphene composite material and preparation method and application thereof |
| CN103290246A (en) * | 2013-05-27 | 2013-09-11 | 南京师范大学 | Preparation method of three-dimensional nano porous tin-base alloy for lithium-ion battery negative electrode |
Non-Patent Citations (2)
| Title |
|---|
| C.Q. ZHANG等: ""Preparation and electrochemical performances of nanoscale"", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| YA YE等: ""Facile synthesis of graphene supported FeSn2"", 《RSC ADVANCES》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107195884A (en) * | 2017-06-01 | 2017-09-22 | 河南理工大学 | A kind of lithium metasilicate doped graphene lithium ion battery negative material and preparation method thereof |
| CN107195884B (en) * | 2017-06-01 | 2019-11-29 | 河南理工大学 | A kind of lithium metasilicate doped graphene lithium ion battery negative material and preparation method thereof |
| CN107799748A (en) * | 2017-10-23 | 2018-03-13 | 天津师范大学 | A kind of nanoscale cube cobaltous stannate and graphene composite material and preparation method and application |
| CN108554434A (en) * | 2018-04-16 | 2018-09-21 | 复旦大学 | Metal@graphitized carbons/graphene complex electrocatalyst materials and preparation method thereof |
| CN108554434B (en) * | 2018-04-16 | 2021-03-30 | 复旦大学 | Metal @ graphitized carbon/graphene composite electrocatalyst material and preparation method thereof |
| CN108597895A (en) * | 2018-06-05 | 2018-09-28 | 哈尔滨工程大学 | A kind of bimetallic oxide and graphene composite material and preparation method thereof |
| CN112331815A (en) * | 2020-11-04 | 2021-02-05 | 四川大学 | Three-dimensional micro-nano composite porous iron-tin-iron-tin nitrogen compound integrated lithium ion battery cathode and one-step preparation method thereof |
| CN112331815B (en) * | 2020-11-04 | 2021-09-10 | 四川大学 | Iron-tin-iron-tin nitrogen compound integrated lithium ion battery cathode and preparation method thereof |
| CN114141992A (en) * | 2021-11-30 | 2022-03-04 | 四川启睿克科技有限公司 | Self-propagating alloyed lithium negative electrode and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106410199B (en) | 2018-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tang et al. | Alkali ions pre-intercalated layered vanadium oxide nanowires for stable magnesium ions storage | |
| CN106410199B (en) | A kind of lithium ion battery graphene/ferro-tin alloy composite negative pole material preparation method | |
| CN104466135B (en) | Method for coating conductive polymer on Ni-Co-Mn acid lithium positive electrode material | |
| CN104051729B (en) | NiFe for cathode of lithium battery2o4the preparation method of/graphene composite material | |
| CN104617271B (en) | Stannic selenide/graphene oxide negative pole composite material for sodium ion battery and preparation method thereof | |
| CN107887587A (en) | Composite cathode material for lithium ion cell and preparation method thereof | |
| CN109326784B (en) | Phosphorus doped MoS2Preparation method and application of loaded graphene nanosheet | |
| Tang et al. | High-performance LiMn2O4 with enwrapped segmented carbon nanotubes as cathode material for energy storage | |
| CN106960954A (en) | A kind of preparation method and application of Prussian blue/graphene/sulphur composite | |
| CN105460917A (en) | Nitrogen-doped carbon nanotube adopting hierarchical structure and preparation method | |
| CN106450265A (en) | In-situ nitrogen-doped carbon coated lithium titanate composite electrode material and preparation method thereof | |
| Sun et al. | In-situ synthesis of graphdiyne on Mn3O4 nanoparticles for efficient Zn ions diffusion and storage | |
| CN110350170A (en) | A kind of preparation method of lithium titanate/graphene composite material | |
| CN109904395A (en) | A kind of molybdenum disulfide-graphene composite material | |
| CN109904400A (en) | A kind of molybdenum disulfide/three-dimensional graphene composite material | |
| CN103682343A (en) | Cobalt stannide/polyaniline composite material, and preparation method and application thereof | |
| CN113644244B (en) | Chromium oxide/carbon fluoride/highly conductive substance composite material for lithium primary battery | |
| CN105789628A (en) | Aza-graphene and manganese dioxide hybrid aerogel, preparation method and application thereof | |
| CN104485443B (en) | A kind of graphene polymer coats the preparation method of niobium cation doping lithium aluminate composite positive pole | |
| CN109904398A (en) | A kind of molybdenum disulfide/graphene composite material | |
| CN104600278A (en) | Preparation method and application of graphene/lithium titanate composite material | |
| CN107017400B (en) | Manganese carbonate/mangano-manganic oxide/graphene trielement composite material preparation method and applications | |
| CN109904396A (en) | A kind of molybdenum disulfide-three-dimensional graphene composite material | |
| CN105789583B (en) | A kind of lithium ion battery negative material Li4Ti5O12/TiO2/ Ag and preparation method thereof | |
| CN109904397A (en) | A kind of molybdenum disulfide/C/ graphene composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |