CN106784596A - One kind prepares binder free Graphene/SnO using laser irradiation original position2The method of combination electrode - Google Patents

One kind prepares binder free Graphene/SnO using laser irradiation original position2The method of combination electrode Download PDF

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Publication number
CN106784596A
CN106784596A CN201611014740.6A CN201611014740A CN106784596A CN 106784596 A CN106784596 A CN 106784596A CN 201611014740 A CN201611014740 A CN 201611014740A CN 106784596 A CN106784596 A CN 106784596A
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sno
laser
graphene
laser irradiation
combination electrode
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陆潇晓
吴国龙
熊琴琴
秦海英
季振国
卿振军
史月琴
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Hangzhou Dianzi University
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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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention discloses one kind and prepares binder free Graphene/SnO using laser irradiation original position2The method of combination electrode.The present invention is by graphene oxide and SnO2Colloidal sol is mixed and made into precursor sol, and colloidal sol is uniformly coated on into copper foil surface, is placed in drying in vacuum drying chamber；According to presoma to Graphene/SnO2The physical parameter selection laser energy density reference value of nano composite material transformation, laser is selected by laser energy density reference value, sets laser technical parameterses；Prefabricated paillon foil is scanned using laser irradiation, the feature of transmutation product is tested, is analyzed, to obtain optimal laser technical parameterses, while logical protective gas reaches in-situ preparation Graphene/SnO to prevent Graphene from aoxidizing2The purpose of nano composite material electrode.Instant invention overcomes conventional graphite alkene/SnO2The defect such as wastage of material, a large amount of waste liquids of generation in composite electrode preparation technology, complicated, the extra addition binding agent of needs of technological process.

Description

One kind prepares binder free Graphene/SnO using laser irradiation original position2Combination electrode Method
Technical field
The present invention relates to one kind binder free Graphene/SnO is prepared using laser irradiation original position2The method of combination electrode.
Background technology
Since being found from 2004, Graphene (Graphene) is unique with it as a kind of new two-dimension nano materials Nanostructured and excellent electricity, magnetics, optics and mechanical property widely paid close attention to.With other carbon simple substance material phases Seemingly, Graphene is difficult to be applied as single material, but is combined by with other materials, can obtain Graphene and be combined Material, has a wide range of applications advance in numerous areas such as semiconductor, biomedicine, catalysis, electrochemistry, energy storage and sensors. Wherein Graphene/SnO2Composite becomes new type lithium ion with advantages such as its functional, cheap, easy preparations The study hotspot in the fields such as cell negative electrode material, electrochemical sensor, electrochemical catalysis.
Traditional Graphene/SnO2The preparation method of composite is relatively complicated, and the preparation technology for generally using at present is The technique of Hydrothermal Synthesiss combination drying and calcination.Due to the technology restriction of Hydrothermal Synthesiss, raw material can not be utilized sufficiently, system Substantial amounts of waste liquid is produced during standby, is not only wasted seriously and is easily polluted environment；And follow-up drying and calcining process takes, consumes Can, the scale application of this kind of high performance negative material is hindered to a certain extent.Hereafter, composite also needs to be made For into electrode, this process needs to mix in composite and a certain proportion of binding agent, conductive agent and organic solvent, is modulated into Slurry is simultaneously brushed in metal foil surfaces such as Copper Foils, and pole plate is made by drying, compacting.The addition of binding agent is likely to result in battery Unstable etc. problem between internal resistance increase, battery performance decline, batch；And what the volatilization of drying process organic solvent was likely to result in Environmental pollution, therefore the preparation technology of electrode also needs upgrading badly.
In recent years, converted by laser induced presoma and chemically reacted, because energy-controllable is good, reproducible, green Environmentally friendly the advantages of, also become the study hotspot for preparing various nano materials.Meanwhile, presoma is directly converted and binder free The proposition of electrode, makes quick, green, inexpensive preparation High-performance graphene/SnO2Composite electrode provides feasibility.
The content of the invention
It is an object of the invention to be directed to the deficiencies in the prior art, there is provided one kind is prepared without viscous using laser irradiation is in situ Knot agent Graphene/SnO2The method of combination electrode.The present invention uses mirror-vibrating optical fiber laser, in the environment of protection gas is connected with To the graphene oxide and SnO that are precoated on copper foil2Collosol intermixture presoma is irradiated.By laser induced light Chemical reaction, makes precursor in situ be converted into Graphene/SnO2Composite, realizes that one-step method prepares Graphene/SnO2Nanometer is multiple Condensation material electrode.Meanwhile, the present invention have studied the relation between laser technical parameterses and composite microstructure, make graphite Alkene/SnO2Composite and its electrode realize green controllable preparation.Binder free Graphene/the SnO obtained using the method2It is multiple Composite electrode shows good cycle performance and specific capacity when being used as the negative material of lithium battery, further proves The feasibility of the scheme of the invention.
In order to solve the above-mentioned technical problem, the present invention is addressed by following technical proposals：
One kind prepares binder free Graphene/SnO using laser irradiation original position2The method of combination electrode, including following step Suddenly：
A. by graphene oxide and SnO2Colloidal sol is mixed and made into precursor sol, and colloidal sol is uniformly coated on into Copper Foil table Face, is placed in drying in vacuum drying chamber；Wherein graphene oxide and SnO2The mass ratio of colloidal sol is 1:8~1:10.
Preferably, the SnO in step A2Colloidal sol, as presoma, is configured to the colloidal sol of transparent clarification using stannous chloride Solution.
Preferably, the precursor colloidal sol in step A needs to add appropriate diluent before coating；Wherein diluent includes The hydrophilic solvents such as ethanol, monoethanolamine.
Preferably, the coating layer weight of copper foil surface is in 1~2mg/cm2。
B. according to presoma to Graphene/SnO2The physical parameter of nano composite material transformation (can be reaction temperature, anti- Stress live energy, reaction time etc.) selection laser energy density reference value, laser is selected by laser energy density reference value, Laser technical parameterses are set, and described laser technical parameterses include optical maser wavelength, laser power, laser relative scanning speed and gather Collection spot diameter；Prefabricated paillon foil is scanned using laser irradiation, the feature of transmutation product is tested, is analyzed, to obtain stone Black alkene/SnO2The optimal laser technical parameterses of nano composite material, while logical protective gas reaches original to prevent Graphene from aoxidizing Position generation Graphene/SnO2The purpose of nano composite material electrode.
Preferably, the selection of laser energy density follows the principle of optimality in step B.When laser energy density is too high, The gasification of coating material will be caused to lose, laser power need to be reduced or sweep speed is improved；When laser energy density is too low, first Driving body colloidal sol can not be converted, it is necessary to improve laser power or reduce sweep speed by effective；When laser energy density is being closed When suitable interval, the energy of acquisition can either order about the conversion of precursor, and the gasification of material can be avoided to lose again, and precursor is swashing Graphene/SnO is transformed under light irradiation2Nano composite material, then in this, as optimum laser energy density setting value；
Wherein described laser energy density computing formula is：PD=P/dv
Wherein, PDIt is the energy density (J/cm of laser2)；P is laser output power (w)；D is laser spot diameter (cm)； V is the sweep speed (cm/s) of laser.In experiment, laser scanning speed, spot diameter and sweep span are fixed to 150mm/s, laser energy density is adjusted by changing laser output power by 120 μm and 100 μm.
Preferably, in step B, laser predose, for the argon for leading to 99% in the atmosphere protection device that placed sample Gas is used as protective gas, and gas washing 2~3 times, to ensure its graphite olefinic constituent not because oxidation and ablation.
C. the test of battery performance：Electrode assembling obtained above is tested into battery into lithium ion, constant current charge and discharge is used The method of electricity is tested battery, to evaluate the capacity and stable charge/discharge of electrode.
Preferably, the constant current charge-discharge speed in step C uses 100mA/g, charge and discharge potential is performed from 0.05-3V Circulation 100 times.
The beneficial effects of the invention are as follows：The prefabricated presoma on Copper Foil is irradiated the invention provides a kind of utilization laser, In copper foil surface in-situ preparation Graphene/SnO2Composite electrode preparation method, overcomes conventional graphite alkene/SnO2Composite wood Wastage of material, a large amount of waste liquids of generation in material technology for preparing electrode, complicated, the extra addition binding agent of needs of technological process etc. are scarce Fall into.When being used as lithium ion battery negative, good cycle performance and specific capacity is shown, with preparation technology letter It is single, low production cost, good stability and the characteristics of use manpower and material resources sparingly.
Brief description of the drawings
Fig. 1 is Graphene/SnO of the present invention2The preparation flow figure of composite electrode；
Fig. 2 is laser irradiating device sketch；
Fig. 3 is preformed electrode, by SnO2The mixed sols that colloidal sol/graphene oxide is made is coated on Copper Foil and dries It is obtained after dry；
Fig. 4 is that sample is 3.33kJ/cm through energy density2,1.67kJ/cm2,0.83kJ/cm2And 0.42kJ/cm2Swash Surface appearance feature figure (SEM figures) after light irradiation；
Fig. 5 is that sample is 3.33kJ/cm through energy density2,1.67kJ/cm2,0.83kJ/cm2And 0.42kJ/cm2Swash X ray diffracting spectrum (XRD) after light irradiation；
Fig. 6 is that sample is subject to energy density for 0.83kJ/cm2Laser irradiation after:A) scanning electron microscopic picture (SEM figures), B) transmission electron microscope picture (TEM figures)；
Fig. 7 is that sample is subject to energy density for 0.83kJ/cm2Laser irradiation after high resolution TEM picture (HRTEM figures)；
Fig. 8 is binder free Graphene/SnO of the present invention2The constant current charge-discharge spectrogram of combination electrode.
Specific embodiment
The present invention is further analyzed with reference to specific embodiment.
Embodiment 1-1, Graphene/SnO2The preparation of composite electrode, such as Fig. 1
A.SnO2The preparation of colloidal sol:It is added in 10ml EGMEs, stannous chloride (2-3g) at 60-70 DEG C Under the conditions of heat and stir 16-24 hours, obtain filemot transparent settled solution.
B. Graphene/SnO2The preparation of precursor sol：0.3-0.5g oxidation stones are added in the solution for obtaining in step Black alkene, stirring and dissolving is uniform.To obtain mixed sols, mixed solution is placed in normal temperature atmospheric environment and is aged in a week.
C. the preparation of preformed electrode:10-20ml monoethanolamines are added in precursor sol prepared by step B, by presoma Collosol coating is tuned into pasty state, and pastel is evenly coated in into copper foil surface using small-sized Cast Strip coating machine, is vacuum dried 2-3 hours, Coating layer weight is made in 1-2mg/cm2Prefabricated paillon foil (Fig. 3).
It is prepared by the D. laser irradiation of electrode:Prefabricated pole piece prepared by step C is placed on the laser irradiating device shown in Fig. 2 In, lead to protective gas argon gas, and gas washing 2-3 times, open laser irradiation nano-graphite.Optical maser wavelength is selected in experiment in 1060- 1080nm optical fiber lasers, the frequency of laser is 20kHZ, and zigzag scanning pattern is performed using vibration mirror scanning case.This implementation The focal length of the laser of example is 301mm, and sweep speed, spot diameter and scanning pattern spacing are fixed to 150mm/s, 120 μm With 100 μm, the laser energy density that four groups of samples are respectively adopted is 3.33kJ/cm2,1.67kJ/cm2,0.83kJ/cm2With 0.42kJ/cm2。
After laser irradiation, the pattern of electrode surface composite is observed and using its microcosmic crystal structure of XRD analysis, to apply Layer pattern is complete and obtains SnO2Nanocrystal as optimum laser energy density selection gist.As shown in figure 3, working as laser work( Rate is more than 0.83kJ/cm2When, coating has significant ablation loss and a cracking phenomena, and with laser power density increase and. And XRD data (Fig. 4) show, when laser power is 0.42kJ/cm2, SnO2Component is presented amorphous state, when laser power is 0.83kJ/cm2When, SnO2It is nanocrystalline to be detected.It is therefore contemplated that Graphene/SnO2Energy prepared by the irradiation of composite laser Metric density optimum value is 0.83kJ/cm2。
Disperse in ethanol, to prepare after being taken off from copper foil surface through the composite coating after optimal parameter laser radiation treatment Its microscopic appearance structure is observed after into high resolution scanning Electronic Speculum (HR-SEM) and transmission electron microscope (TEM) sample.As shown in figure 5, The laminated structure and nano particle of Graphene are clear and legible, show typical Graphene/SnO2The microscopic appearance of composite Feature.The SnO under high resolution TEM (Fig. 6)2Particle can be recognized clearly by its spacing of lattice.Fig. 7 is sample It is 0.83kJ/cm by energy density2Laser irradiation after high resolution TEM picture (HRTEM figures).
Embodiment 1-2, Graphene/SnO2The storage lithium performance test of composite electrode
Binder free Graphene/SnO2 combination electrodes obtained in embodiment 1 are cut into the disk of a diameter of 15mm, is selected Standard lithium ion battery electrolytic solution (EC：DMC=1：1, LiPF6 concentration is 1mol/L) and lithium metal paillon foil as to electrode, RC2030 type button cells are assembled into argon gas gloves for protection case, carrying out constant current in Neware BTS battery test systems fills Discharge test.Test parameter is:Charge-discharge velocity 100mA/g, charge and discharge potential performs circulation 100 times from 0.05-3V.
(Fig. 8) is learnt with reference to the capacity versus cycle number of times collection of illustrative plates of battery, when the electrode is used as lithium ion battery negative, performance Go out good lithium storage content and cycle life (in the case where charge-discharge velocity is 100mA/g, still can protect after circulation 100 times Hold the specific capacity of about 610mAh/g).Obtained binder free Graphene/SnO of the invention2Combination electrode has good discharge and recharge Performance and lithium storage content, overcome conventional graphite alkene/SnO2Wastage of material, generation in composite electrode preparation technology is a large amount of Waste liquid, technological process are complicated, with preparation process is simple, low production cost, good stability and the characteristics of use manpower and material resources sparingly.
In a word, the above lithium battery applications is only presently preferred embodiments of the present invention, all according to scope of the present invention patent The impartial change made and modification, should all belong to the covering scope of patent of the present invention.

Claims (6)

1. it is a kind of to prepare binder free Graphene/SnO using laser irradiation original position2The method of combination electrode, it is characterised in that the party Method is specifically：
Step (1), by graphene oxide and SnO2Colloidal sol is mixed and made into precursor sol, and colloidal sol is uniformly coated on into Copper Foil table Face, is placed in drying in vacuum drying chamber；Wherein graphene oxide and SnO2The mass ratio of colloidal sol is 1:8~1:10；
Step (2), according to presoma to Graphene/SnO2The physical parameter selection laser energy density of nano composite material transformation Reference value, laser is selected by laser energy density reference value, sets laser technical parameterses；Wherein laser technical parameterses include Optical maser wavelength, laser power, laser relative scanning speed and aggregation spot diameter；Prefabricated paillon foil is scanned using laser irradiation, The feature of transmutation product is tested, is analyzed, to obtain Graphene/SnO2The optimal laser technology ginseng of nano composite material Number, while logical protective gas obtains generated in-situ Graphene/SnO to prevent Graphene from aoxidizing2Nano composite material.
2. one kind as claimed in claim 1 prepares binder free Graphene/SnO using laser irradiation original position2The side of combination electrode Method, it is characterised in that the SnO in step (1)2Colloidal sol is prepared using stannous chloride as raw material.
3. one kind as claimed in claim 1 prepares binder free Graphene/SnO using laser irradiation original position2The side of combination electrode Method, it is characterised in that the precursor sol in step (1) needs to add diluent before coating；Wherein diluent includes ethanol, second The hydrophilic solvents such as hydramine.
4. one kind as claimed in claim 1 prepares binder free Graphene/SnO using laser irradiation original position2The side of combination electrode Method, it is characterised in that the coating layer precursor sol weight of step (1) copper foil surface is 1~2mg/cm2。
5. one kind as claimed in claim 1 prepares binder free Graphene/SnO using laser irradiation original position2The side of combination electrode Method, it is characterised in that step (2) presoma is to Graphene/SnO2The physical parameter of nano composite material transformation includes reaction temperature Degree, Activation energy, reaction time.
6. one kind as claimed in claim 1 prepares binder free Graphene/SnO using laser irradiation original position2The side of combination electrode Method, it is characterised in that the laser energy density computing formula described in step (2) is：PD=P/dv；
Wherein, PDIt is the energy density (J/cm of laser2)；P is laser output power (w)；D is laser spot diameter (cm)；V is The sweep speed (cm/s) of laser.
CN201611014740.6A 2016-11-18 2016-11-18 One kind prepares binder free Graphene/SnO using laser irradiation original position2The method of combination electrode Pending CN106784596A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108767240A (en) * 2018-06-11 2018-11-06 佛山腾鲤新能源科技有限公司 A kind of preparation method of lithium ion battery negative material
CN109037645A (en) * 2018-08-09 2018-12-18 哈尔滨工业大学 The method that one step prepares metal oxide@chlorine doped graphene lithium ion battery negative material
CN109081369A (en) * 2018-07-16 2018-12-25 杭州电子科技大学 It is a kind of to prepare SnO using colloidal sol steam fog auto-combustion method2The method of the nano combined bead of amorphous carbon
CN109686593A (en) * 2019-01-17 2019-04-26 西安交通大学 One kind is based on secondary laser irradiation preparation MnO2The method of/graphene combination electrode
CN110165142A (en) * 2019-04-17 2019-08-23 杭州电子科技大学 A method of nanometer combined electrode material is prepared in situ
CN110660926A (en) * 2018-06-28 2020-01-07 Tcl集团股份有限公司 Novel transparent conductive film and preparation method and application thereof
CN112723855A (en) * 2019-10-14 2021-04-30 武汉大学 Laser engraving preparation method and application of graphene-ceramic composite electrode array
CN114005963A (en) * 2021-11-02 2022-02-01 北京化工大学 Modification method of graphite negative plate of lithium ion battery

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CN103854880A (en) * 2012-11-30 2014-06-11 海洋王照明科技股份有限公司 Graphene electrode sheet and preparation method and application thereof
CN105895384A (en) * 2016-05-10 2016-08-24 济南大学 Method for preparing graphene/ superfine cobalt oxide granule compound electrode material
CN106098410A (en) * 2016-06-25 2016-11-09 于有海 Laser one-step method prepares ultracapacitor Graphene/manganese oxide flexible electrode

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CN103854880A (en) * 2012-11-30 2014-06-11 海洋王照明科技股份有限公司 Graphene electrode sheet and preparation method and application thereof
CN105895384A (en) * 2016-05-10 2016-08-24 济南大学 Method for preparing graphene/ superfine cobalt oxide granule compound electrode material
CN106098410A (en) * 2016-06-25 2016-11-09 于有海 Laser one-step method prepares ultracapacitor Graphene/manganese oxide flexible electrode

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108767240A (en) * 2018-06-11 2018-11-06 佛山腾鲤新能源科技有限公司 A kind of preparation method of lithium ion battery negative material
CN108767240B (en) * 2018-06-11 2021-03-19 河源云创新能源实业有限公司 Preparation method of lithium ion battery negative electrode material
CN110660926A (en) * 2018-06-28 2020-01-07 Tcl集团股份有限公司 Novel transparent conductive film and preparation method and application thereof
CN109081369A (en) * 2018-07-16 2018-12-25 杭州电子科技大学 It is a kind of to prepare SnO using colloidal sol steam fog auto-combustion method2The method of the nano combined bead of amorphous carbon
CN109081369B (en) * 2018-07-16 2020-11-17 杭州电子科技大学 SnO prepared by sol-vapor self-combustion method2Method for producing amorphous carbon nanocomposite pellets
CN109037645A (en) * 2018-08-09 2018-12-18 哈尔滨工业大学 The method that one step prepares metal oxide@chlorine doped graphene lithium ion battery negative material
CN109037645B (en) * 2018-08-09 2021-07-20 哈尔滨工业大学 Method for preparing metal oxide @ chlorine-doped graphene lithium ion battery anode material in one step
CN109686593A (en) * 2019-01-17 2019-04-26 西安交通大学 One kind is based on secondary laser irradiation preparation MnO2The method of/graphene combination electrode
CN110165142A (en) * 2019-04-17 2019-08-23 杭州电子科技大学 A method of nanometer combined electrode material is prepared in situ
CN112723855A (en) * 2019-10-14 2021-04-30 武汉大学 Laser engraving preparation method and application of graphene-ceramic composite electrode array
CN112723855B (en) * 2019-10-14 2022-03-04 武汉大学 Laser engraving preparation method and application of graphene-ceramic composite electrode array
CN114005963A (en) * 2021-11-02 2022-02-01 北京化工大学 Modification method of graphite negative plate of lithium ion battery

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