CN108183205A - A kind of sodium-ion battery flexible self-supporting electrode material and its application and preparation method - Google Patents

A kind of sodium-ion battery flexible self-supporting electrode material and its application and preparation method Download PDF

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CN108183205A
CN108183205A CN201711332068.XA CN201711332068A CN108183205A CN 108183205 A CN108183205 A CN 108183205A CN 201711332068 A CN201711332068 A CN 201711332068A CN 108183205 A CN108183205 A CN 108183205A
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sodium
electrode
rgo
ion battery
flexible self
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朱窈瑶
王睿
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China Aviation Lithium Battery Co Ltd
China Aviation Lithium Battery Jiangsu Co Ltd
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China Aviation Lithium Battery Jiangsu Co Ltd
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/054Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/058Construction or manufacture
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention relates to chemical cell field, especially a kind of active material of embedded type storage sodium mechanism is as sodium-ion battery flexible self-supporting electrode material and its application and preparation method;The electrode material includes the two-dimensional slice structural material Ti with sodium ion insertion ability3C2The fexible film composite material prepared with rGO;It is of the invention that difference lies in apply a kind of nontoxic two-dimensional slice structural material Ti of novel environment friendly with other sodium ion negative materials3C2As electroactive material, prepare fexible film composite material by being combined with rGO and make flexible self-supporting electrode material, without collector, binding agent and conductive additive;Therefore, there is high mass energy density, long circulation life, good high rate performance.Meanwhile Ti3C2The fexible film composite material of@rGO makees flexible self-supporting electrode material with bent, environmentally friendly, inexpensive advantage;Battery packaging technology will be also greatly simplified, efficiency is improved, reduces cost, be with a wide range of applications in bent electronic product energy storage field.

Description

A kind of sodium-ion battery flexible self-supporting electrode material and its application and preparation method
Technical field
The present invention relates to chemical cell field, especially a kind of active material of embedded type storage sodium mechanism is as sodium ion electricity Pond flexible self-supporting electrode material and its application and preparation method.
Background technology
Energy storage technology is all kinds of energy application demands of balance, promotes the effective means of social integral energy service efficiency, The applications such as extensive and distribution type renewable energy utilization, the exploration of urban distribution network peak load shifting, portable electronic product, the outer space One of field all has wide practical use, while be also the critical support technology of intelligent grid construction.In all kinds of energy storage technologies In, the carrier of electrochemical energy storage is battery, in existing energy-storage battery system, lithium ion battery with its material system flexibly, skill Art updating decision becomes energy-storage battery system of greatest concern, the extensive use in all kinds of demonstration projects.But current lithium ion Cell safety problem not yet solves at all, and battery cost is higher, and with scale energy storage and the popularization of electric vehicle engineering Using lithium ion battery will be likely to be encountered the bottleneck of lithium resource shortage in future.As the metallic element of the same clan with elemental lithium, sodium It is closer to every physicochemical properties of lithium, contains abundant (elements of earth's crust reserves the 4th) in nature, reserves are far high In focusing primarily upon the lithium resource in South America, and be easy to purify, there is inborn cost advantage.Meanwhile most of existing sodium from Sub- battery material system operating voltage range is consistent with water burning voltage window, and use can be matched with water phase electrolyte, has first It security advantages.
At the end of the 20th century at the beginning of 21 century, world's main economic body has launched respectively battery technology development plan, in all kinds of rule Sodium-ion battery is all classified as medium-long term target in drawing, but actually the reaction mechanism of sodium-ion battery and material crystal structure with Lithium ion battery it is similar, it is existing that material system matching principle and tackling problems in key technologies route can also use for reference lithium ion battery Experience, so, technological break-through and product maturation time may be shorter than expected.At present, some battery technologies are more first in the world Into country sodium-ion battery technology has been classified as an important basic and perspective study field, and as future emphasis The energy storage electrochemical techniques developing direction of concern.Wherein, the U.S. and Japan set up special support sodium-ion battery technology in the recent period Pilot study early period, China starts late in this respect, it is necessary to step up into line trace and the relevant technologies deposit.Sodium ion electricity Although pond obtains the favor of domestic and foreign scholars in recent years, the energy storage system new as one, the key of sodium-ion battery development It is the research of novel high-performance positive and negative pole material and electrolyte, Research foundation and commercialized development based on lithium ion battery are gone through Journey, anode material of lithium-ion battery research relatively lag behind, and seriously constrain the practical application of sodium-ion battery.It studies at present more Negative material mainly have:Carbon-based material, metal oxide, alloy etc..
Due to successful application of the graphite cathode in lithium ion battery, people generally have an optimistic view of carbon-based material in sodium-ion battery In utilization.Research shows that graphite cathode can not meet the needs of embedding sodium, thus capacity pole due to the limitation of interlamellar spacing It is low.It is that the carbon materials of various non-graphite structures shows the reversible deintercalation performance of good sodium ion, wherein hard carbon material instead It can be most prominent.Hard carbon material has macroscopical non-graphite structure, while includes graphite interlayer again in microstructure, such as:Resin carbon, Carbon black etc..The hard carbon material of Komaba seminars report is in 25mAg-1There is down 240mAhg-1Embedding capacity, 100 times cycle After be maintained at 200mAhg-1, there is preferable cycle performance.Hard carbon material presently, there are the problem of be first circle coulombic efficiency it is low, High rate performance is poor, cycle life is short.Mainly with metallic sodium reversible redox reaction occurs for transition metal oxide, so far for Only, the transition metal oxide for sodium-ion battery motor material is also fewer, and negative material mainly has:TiO2、α-MoO3 Deng.The problem of being primarily present includes that reversible capacity is smaller, cyclical stability is poor.Alloy type material is due to having higher theoretical ratio Capacity is increasingly becoming research hotspot, and sodium can form intermetallic compound at room temperature with various metals, and research has shown that Na can be with Sn, Sb, Ge, Pb etc. are respectively formed alloy Na15Sn4、Na3Sb、Na3Ge and Na15Pb4, by calculating, corresponding theoretical specific capacity It is 845,660,1108 and 485mAhg respectively-1, but alloy type material generally existing during reversible deintercalation sodium is irreversible Volume expansion, lead to that capacity attenuation is fast, cyclical stability is poor, cycle life is short.The research of sodium-ion battery has been in step Section, the above material are also faced with much challenging before practical application.It is really suited for commercialized sodium-ion battery cathode Material needs to meet requirement as described below:Inexpensive, safe and non-toxic, good chemical property.
Embedded type anode material of lithium-ion battery is considered great development prospect, and it is special that insertion-host electrode materials generally have Lamellar structure, sodium ion can reversible insertion emerge in interlayer and do not destroy its structure, therefore with long circulation life and good High rate performance.
Recently, Gogotsi etc. reports a series of special compounds, they have two-dimensional slice structure and have good Electric conductivity is named as MXenes according to element composition.The series compound be " A " layer atom in MAX phases is passed through it is wet The method of chemistry removes and obtains the MXenes of two-dimensional slice structure, can use Mn+1AXnIt representing, wherein M represents transition metal, A typically represents third and fourth major element, such as:Al, Ga, Si or Ge;X is C or N.MXenes series compounds are to pass through MAX powder containing Al is immersed in dense HF solution, Al atoms therein are etched away in room temperature or slightly at a temperature of heating, Such as: Ti3C2, Ti2C, Ti4C3, TiNbC and (V0.5Cr0.5)3C2Deng.The method of HF etchings makes a large amount of O of MXenes adsorptions, OH and the functional group containing F, this MXene containing surface functional group are usually used
Mn+1XnTXIt represents, wherein T represents surface functional group, and x represents the quantity of end group.
In recent years, using Gogotsi seminars as representative, domestic and international researcher is to MXenes series compounds from theory It calculates practical application and has carried out systematic research:1st, the interlayer of two-dimensional slice structure MXenes can be embedded in organic macromolecular and close Object, such as:Hydrazine, DMSO and urea molecule;2nd, two-dimensional slice structure MXenes also have reversible embedding lithium characteristic, can be used as lithium from Sub- cell negative electrode material when being prepared into additive-free self-supporting electrode, has 410mAhg under 1C-1Discharge capacity.3rd, it is more Kind cation in aqueous solution can spontaneous reversible insertion, abjection MXene interlayers, such as:Li+, Na+, Mg2+, K+, NH4 +And Al3+, There is good chemical property in aqueous electrolyte system.4th, it is proved by first principle Density function theory:Na+、K+、Ca2+MXenes interlayers can be embedded in, with Ti3C2For, the theoretical specific capacity of Na, K, Ca is respectively 351.8,191.8, 319.8mAhg-1, compared with existing lithium/anode material of lithium-ion battery, MXenes has a good application prospect.
It is demonstrated experimentally that Ti3C2Good chemical property is shown as lithium ion battery negative material;It is counted by theory It calculates, Ti3C2It can realize the reversible embedding de- of sodium ion.But Na+Ionic radius be much larger than Li+, to realize that sodium ion is reversible It is embedding de-, higher requirement will be proposed to two-dimensional layer material.Document report, increase graphene sheet layer interlamellar spacing can make it have Embedding sodium activity.Similarly, increase Ti3C2Lamella interlamellar spacing is conducive to the reversible embedding de- of sodium ion, and still, increased interlamellar spacing will be led It causes the Van der Waals force between lamella fainter, interlayer electric conductivity is made to be deteriorated.
Invention content
The purpose of the present invention is:Overcome deficiency of the prior art, provide a kind of with high-energy density, the cycle of length The sodium-ion battery in service life flexible self-supporting electrode material, i.e. Ti3C2@rGO composite and flexible self-supporting electrode materials;The present invention Another purpose be:The application of sodium-ion battery flexible self-supporting electrode material is provided, invention is there are one purpose: A kind of preparation method of sodium-ion battery flexible self-supporting electrode material is provided.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:
A kind of sodium-ion battery flexible self-supporting electrode material, the electrode material include having sodium ion embedding energy The two-dimensional slice structural material Ti of power3C2The Ti prepared with rGO3C2@rGO fexible film composite materials.
Preferably, the Ti3C2Interlamellar spacing and lamella part lift-off processing first are enlarged with DMSO, by DMSO processing Ti3C2It is scattered in distilled water, adds in appropriate GO solution, ultrasonic disperse prepares Ti3C2It with GO suspension, is filtered by vacuum, gained is thin Film is air-dried in shady place;By gained Ti3C2@GO films obtain Ti with the method for gas phase hydrazine hydrate low-temperature reduction3C2@rGO flexible thins Film.
Preferably, the Ti3C2In@rGO fexible film composite materials, Ti3C2Mass fraction is more than 80%.
Preferably, the Ti3C2It is made of less than 10 layers or more 50 layers lamellar structures.
Preferably, the rGO is obtained by hydrazine hydrate low-temperature gaseous phase reduction GO.
Preferably, the electro-chemical activity test point position section of the sodium-ion battery is 0-3V.
Preferably, the electrode material is used as the cathode of battery.
A kind of sodium-ion battery is assembled into half electricity of sodium ion with flexible self-supporting electrode material under organic electrolyte system The application in pond.
A kind of preparation method of sodium ion half-cell, it is characterised in that:The preparation method includes the following steps:With Ti3C2 The Ti prepared with rGO3C2@rGO fexible films composite material is active material, and direct clip size and the moderate film of quality are made Pole piece;Sodium piece is used as to electrode, and glass fibre membrane (GF/D whatman) is as diaphragm, the NaClO of 1mol/L4It is dissolved in carbon Make electrolyte in acid propylene ester (PC), be assembled into sodium ion half-cell.
The advantageous effect of technical solution using the present invention is:
It is of the invention that difference lies in apply a kind of nontoxic two-dimensional slice of novel environment friendly with other sodium ion negative materials Structural material Ti3C2As electroactive material, prepare fexible film composite material by being combined with rGO and make flexible self-supporting electrode Material, without collector, binding agent and conductive additive;Therefore, there is high mass energy density, long circulation life, good Good high rate performance.Meanwhile Ti3C2The fexible film composite material of@rGO makees flexible self-supporting electrode material with bent, nothing Poison, environmental protection, low cost, the advantage for being easy to large-scale production;To also greatly simplify battery packaging technology, improve efficiency, reduce into This, is with a wide range of applications in bent electronic product energy storage field.
Description of the drawings
The present invention is further described with reference to the accompanying drawings and examples.
Fig. 1 is the Ti that embodiment 1,2 obtains3C2With with the processed Ti of DMSO3C2Scanning electron microscope (SEM) photograph;
Fig. 2 is the Ti that embodiment 1 obtains3C2XRD spectrum;
Fig. 3 is the Ti that embodiment 6 obtains3C2The scanning electron microscope (SEM) photograph of the fexible film composite material of@rGO;
Fig. 4 is the Ti that embodiment 1,2,6 obtains3C2, with the processed Ti of DMSO3C2And Ti3C2The fexible film of@rGO The electro-chemical test collection of illustrative plates of composite material;
Fig. 5 is the Ti that embodiment 6 obtains3C2The fexible film composite material pictorial diagram of@rGO.
Specific embodiment
In conjunction with the accompanying drawings, the present invention is further explained in detail.These attached drawings are simplified schematic diagram, only with Illustration illustrates the basic structure of the present invention, therefore it only shows composition related to the present invention.
Hereinafter, the present invention gives following embodiment and is described with reference to the drawings.However the present invention is not limited to these Examples. The various values and material used in these embodiments are illustrative.Description carries out in the following order:
1st, according to the embodiment of the present invention the whole description of electrode material, electrode and half-cell
2nd, embodiment 1 (electrode material and electrode according to the embodiment of the present invention)
3rd, embodiment 2 (improvement of electrode material and electrode prepared in embodiment 1)
4th, embodiment 3 (variation of the electrode material in 2 and electrode according to an embodiment of the invention)
5th, embodiment 4 (variation of half-cell prepared in 2 according to an embodiment of the invention)
6th, embodiment 5 (variation of half-cell prepared in 3 according to an embodiment of the invention)
7th, embodiment 6 (electrode material and electrode according to the embodiment of the present invention)
8th, embodiment 7 (variation of the electrode material in 6 and electrode according to an embodiment of the invention)
9th, embodiment 8 (variation of half-cell prepared in 6 according to an embodiment of the invention)
10th, embodiment 9 (variation of half-cell prepared in 7 according to an embodiment of the invention)
[whole description of electrode material according to the embodiment of the present invention, electrode and battery]
According to the embodiment of the present invention electrode material, in electrode and battery, Ti3C2Two-dimensional slice structural material and Ti3C2The composite and flexible self-supporting material of@rGO can realize the reversible embedded abjection of sodium ion in organic electrolyte system; Wherein Ti3C2It is independent electro-chemical activity phase, chemical composition contains titanium and carbon, has the two-dimensional slice knot of class graphite Structure, layer is interior to be combined in the form of covalent bond, and interlayer is interacted with Van der Waals force, forms indefinite form titanium carbide, and chemical formula has Basic stoicheiometry form Ti3C2;RGO does not have storage sodium activity, can build conductive network, bridge multiple Ti3C2Particle carries High conduction performance.In the examples below that, electroactive material is respectively Ti3C2Powder, DMSO treated Ti3C2Powder, DMF Treated Ti3C2Powder, Ti3C2@GO fexible film composite materials.
According to the embodiments of the present invention for including above-mentioned preferred embodiment, relative to the sodium ion electricity of standard hydrogen electrode The electroactive potential region in pond is 0-3V.
According to the preparation of the battery of the embodiments of the present invention including above-mentioned preferred embodiment and packaging technology: Ti3C2@ The composite and flexible self-supporting material of rGO is active material, and direct clip size and the moderate film of quality make pole piece, without other Additive and collector.Sodium piece is used as to electrode, and glass fibre membrane (GF/D whatman) is as diaphragm, the NaClO of 1mol/L4 It is dissolved in propene carbonate (PC) and makees electrolyte, be assembled into 2032 button cells.
According to the preparation of the electrode material of the embodiments of the present invention including above-mentioned preferred embodiment:Used in the present invention Chemical reagent is untreated street drug.Multilayer two-dimension lamellar structure Ti3C2Preparation method: Ti3AlC2It is accurate to claim Amount 1g is poured into plastic bottle with cover, and graduated cylinder measures the dense HF of 10mL (Nanjing Chemistry Reagent Co., Ltd., >=40.0%), slowly falls Enter plastic bottle, cover bottle cap and 18h is stirred at room temperature, centrifuge, gained precipitation is washed with distilled water, 80 DEG C of vacuum drying chamber is dry Dry 12h, it is spare.The increased two-dimensional slice structure Ti of interlamellar spacing3C2Preparation method:Ti as obtained by by back3C2With 18h is stirred at room temperature in DMSO (Nanjing Chemistry Reagent Co., Ltd.), centrifuges, precipitation absolute ethyl alcohol and distilled water are repeatedly washed It washs, the dry 12h of 80 DEG C of vacuum drying chamber.Ti3C2The preparation method of@rGO composite and flexible films:The Ti that will be handled with DMSO3C2 It is scattered in distilled water, adds in appropriate GO solution, ultrasonic disperse prepares Ti3C2With GO suspension, vacuum filtration, gained film exists Shady place air-dries.By gained Ti3C2@GO films obtain Ti with the method for gas phase hydrazine hydrate low-temperature reduction3C2@rGO fexible films. Ti3C2In rGO fexible film composite materials, Ti3C2Mass fraction is more than 80%;Wherein, Ti3C2Particle has 10 layers or more 50 The following lamellar structure of layer is formed.
The half-cell that an implementation according to the present invention provides, the battery include anode, which includes having sodium Ion reversible is embedded in the Ti of abjection ability3C2The electrode material of two-dimensional slice structure has the reversible embedded abjection ability of sodium ion With the processed Ti of DMSO3C2The electrode material of two-dimensional slice structure, have the reversible embedded abjection ability of sodium ion at DMF The Ti managed3C2The electrode material of two-dimensional slice structure, the Ti with the reversible embedded abjection ability of sodium ion3C2@rGO flexible thins Film composite material.
The electrode material provided in the present invention includes the Ti with the reversible embedded abjection ability of sodium ion3C2Two-dimensional slice knot Structure material, with the processed Ti of DMSO3C2Two-dimensional slice structural material, with the processed Ti of DMF3C2Two-dimensional slice structural wood Material, Ti3C2@rGO fexible film composite materials make flexible self-supporting electrode.
Embodiment 1
The electrode material prepared in embodiment 1 includes the Ti with the reversible embedded abjection ability of sodium ion3C2Two-dimensional slice knot Structure material.
According to above-mentioned whole description multilayer two-dimension lamellar structure Ti3C2The preparation method of electrode material, electrode and half-cell, Electrode material, electrode and the half-cell needed for embodiment 1 are prepared, it is spare.
Ti is characterized by scanning electron microscope3C2Micro-structure, scanning electron microscope used in the present invention is Field emission scanning electron microscope (FESEM, LEO1430VP, Germany).Such as Fig. 1 a, shown in b, what dense HF was etched Ti3C2For irregular particle, each particle is made of the lamellar structure of class sandwich, there is clear boundary line between piece and piece.
The storage sodium activity of the test material is assessed by electro-chemical test, battery test apparatus used in the present invention is Land 2001A cell testers.Such as Fig. 4 a, b, shown in d, the respectively Ti of multilayer two-dimension lamellar structure3C2Make sodium-ion battery The first circle charge and discharge for the half-cell that cathode is assembled, cycle life and high rate performance figure.Its first circle specific discharge capacity is 153.2mAh g-1, first circle coulombic efficiency is only 47.91%;Second circle specific discharge capacity is 60.7mAh g-1, after cycle 50 is enclosed Specific discharge capacity is 56.4mAh g-1;Current density is 50 mA g-1When, specific discharge capacity is 59.6mAh g-1, current density Increase to 2000mAg-1When, specific discharge capacity is 26.7mAh g-1, current density is reduced to 50mA g-1, specific discharge capacity recovery To 56.9mAh g-1
Embodiment 2
The electrode material prepared in embodiment 2 includes processed with the reversible embedded abjection ability DMSO of sodium ion Ti3C2Two-dimensional slice structural material.
According to the increased two-dimensional slice structure Ti of above-mentioned whole description interlamellar spacing3C2Electrode material, electrode and half-cell Preparation method prepares electrode material, electrode and half-cell needed for embodiment 2, spare.
The increased two-dimensional slice structure Ti of interlamellar spacing is observed by scanning electron microscope3C2Micro-structure, such as Fig. 1 c, d It is shown, compared with sample in embodiment 1, with the Ti of DMSO processing3C2Interlamellar spacing significantly become larger, occur between piece and piece notable Slit.
The Ti of DMSO processing3C2Chemical property such as Fig. 4 a, b, shown in d, first circle specific discharge capacity is 480.3 mAh g-1, First circle coulombic efficiency is 43.81%;Second circle specific discharge capacity is 272mAh g-1, specific capacity is 201.8mAh after cycle 50 is enclosed g-1;Current density is 50mAg-1When, specific discharge capacity is 192.2mAh g-1, current density increases to 2000mA g-1When, electric discharge Specific capacity is 47.9mAh g-1, current density is reduced to 50mA g-1, specific discharge capacity is restored to 174.5mAhg-1
Embodiment 3
The present embodiment place different from embodiment 2 is to handle Ti using organic solvent DMF3C2, remaining and embodiment 2 is identical.
Embodiment 4
The electrode material prepared in embodiment 4 includes the Ti with DMSO with the reversible embedded abjection of sodium ion3C2Two dimension Lamellar structure material.
According to the increased two-dimensional slice structure Ti of above-mentioned whole description interlamellar spacing3C2Electrode material, electrode preparation side Method prepares electrode material, electrode needed for embodiment 4.Prepared electrode is anode, and sodium piece is used as to electrode, glass fibre Film (GF/D whatman) is as diaphragm, the NaClO of 1mol/L4Be dissolved in propene carbonate (PC) and ethylene carbonate (EC) with Volume fraction 1:Make electrolyte in the solution of 1 mixing, be assembled into 2032 type button cells.
The first circle specific discharge capacity of battery is 434.6mAh g in embodiment 4-1, first circle coulombic efficiency is 38.57%;The Two circle specific discharge capacities are 202.84mAh g-1, specific capacity is 185.8mAh g after cycle 50 is enclosed-1;Current density is 50mA g-1 When, specific discharge capacity is 172.9mAh g-1, current density increases to 2000 mAg-1When, specific discharge capacity is 26.5mAh g-1, Current density is reduced to 50mAg-1, specific discharge capacity is restored to 174.5mAh g-1
Embodiment 5
The present embodiment place different from embodiment 4 is to substitute DMSO processing Ti using organic solvent DMF3C2, remaining It is same as Example 4.
Embodiment 6
The electrode material prepared in embodiment 6 is included with the reversible embedded abjection ability of sodium ion
Ti3C2@rGO composite and flexible films.
According to Ti in above-mentioned whole description3C2@rGO composite and flexibles films and Ti3C2@rGO composite and flexibles film is used as from branch The production method for supportting electrode assembling half-cell prepares electrode material, electrode and half-cell needed for embodiment 6.
Ti is observed by scanning electron microscope3C2The microscopic appearance and structure of@rGO composite and flexible films, as shown in figure 3, Fig. 3 a, b Ti2C3The positive scanning electron microscope (SEM) photograph of@GO composite and flexible films, it can be seen that Ti2C3It is thin that particle is evenly distributed on GO In film, GO lamellas also soilless sticking phenomenon;Fig. 3 c, d Ti2C3The scanning electron microscope (SEM) photograph of@GO side surface of thin film, the thickness of composite and flexible film Degree is about 100um, and side partial enlarged view further illustrates Ti2C3It is particle studded between GO lamellas.
Ti is characterized by electro-chemical test2C3@GO composite and flexible films make the electricity of the anode material of lithium-ion battery of self-supporting Chemical property, as shown in figure 4, first circle specific discharge capacity is 382.5mAh g in Fig. 4 a-1, first circle coulombic efficiency is 28.14%;Figure Shown in 4b, the second circle specific discharge capacity is 142mAh g-1, 30 circle capacity maintain 150mAh g before cycle-1Left and right, after 30 enclose Capacity gradually increases, and capacity stabilization is in 220mAh g after being enclosed to 40-1, recycle 50 circle capacity and be maintained at 222.9Ah g-1, capacity without Attenuation;Fig. 4 c are Ti2C3When@GO composite and flexible films make anode material of lithium-ion battery, the service life of the circle of charge and discharge cycles 200 Figure, 200 circle capacity of cycle is undamped, and specific discharge capacity is 258.4mAh g-1.Preceding 40 enclose the process slowly to activate, specific capacity Slowly increase, coulombic efficiency is gradually lowered to 100% by 129%, and is stably maintained at 100% in subsequent charge and discharge cycles Left and right;From Fig. 4 d as it can be seen that current density is 50mAg-1When, specific discharge capacity is 247.5mAh g-1, current density increases to 2000mAg-1When, specific discharge capacity is only 8mAh g-1, current density is reduced to 50mA g-1, specific discharge capacity is restored to 251.8mAh g-1
Embodiment 7
The present embodiment place different from embodiment 6 is to substitute DMSO processing Ti with organic solvent DMF3C2, remaining It is same as Example 6.
Embodiment 8
The electrode material prepared in embodiment 8 is included with the reversible embedded abjection ability of sodium ion
Ti3C2@rGO composite and flexible films.
According to Ti in above-mentioned whole description3C2The production method of@rGO composite and flexible films prepares the electricity needed for embodiment 6 Pole material.Prepared electrode is anode, and sodium piece is as cathode, and glass fibre membrane (GF/D whatman) is as diaphragm, 1mol/ The NaClO of L4Propene carbonate (PC) and ethylene carbonate (EC) are dissolved in volume fraction 1:It is electrolysed in the solution of 1 mixing Liquid is assembled into 2032 button cells.
The first circle specific discharge capacity of battery is 364.6mAh g in embodiment 8-1, first circle coulombic efficiency is 22.17%;Two circles Specific discharge capacity is 112.88mAh g-1, equally irised out preceding 40 and showed electro-active phenomenon, specific capacity is after 50 circle of cycle 195.2mAh g-1;Current density is 50mA g-1When, specific discharge capacity is 172.9mAh g-1, current density increases to 2000mA g-1When, specific discharge capacity is 9.5mAh g-1, current density is reduced to 50mA g-1, specific discharge capacity is restored to 171.2mAh g-1
Embodiment 9
The present embodiment place different from embodiment 8 is to substitute DMSO processing Ti with organic solvent DMF3C2, remaining It is same as Example 8.
Using above-mentioned desirable embodiment according to the present invention as enlightenment, by above-mentioned description, relevant staff is complete Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention Property range is not limited to the content on specification, it is necessary to determine its technical scope according to right.

Claims (9)

1. a kind of sodium-ion battery flexible self-supporting electrode material, it is characterised in that:The electrode material includes having sodium Ion is embedded in the two-dimensional slice structural material Ti of ability3C2The Ti prepared with rGO3C2@rGO fexible film composite materials.
2. a kind of sodium-ion battery flexible self-supporting electrode material according to claim 1, it is characterised in that:It is described Ti3C2Interlamellar spacing and lamella part lift-off processing first are enlarged with DMSO, by the Ti of DMSO processing3C2It is scattered in distilled water, Appropriate GO solution is added in, ultrasonic disperse prepares Ti3C2With GO suspension, vacuum filtration, gained film is air-dried in shady place;By institute Obtain Ti3C2@GO films obtain Ti with the method for gas phase hydrazine hydrate low-temperature reduction3C2@rGO fexible films.
3. a kind of sodium-ion battery flexible self-supporting electrode material according to claim 1, it is characterised in that:It is described Ti3C2In@rGO fexible film composite materials, Ti3C2Mass fraction is more than 80%.
4. a kind of sodium-ion battery flexible self-supporting electrode material according to claim 1, it is characterised in that:It is described Ti3C2It is made of less than 10 layers or more 50 layers lamellar structures.
5. a kind of sodium-ion battery flexible self-supporting electrode material according to claim 1, it is characterised in that:It is described RGO is obtained by hydrazine hydrate low-temperature gaseous phase reduction GO.
6. a kind of sodium-ion battery flexible self-supporting electrode material according to claim 1, it is characterised in that:The sodium The electro-chemical activity test point position section of ion battery is 0-3V.
7. a kind of sodium-ion battery flexible self-supporting electrode material according to claim 1, it is characterised in that:The electricity Pole material is used as the cathode of battery, without collector, binding agent and conductive agent.
8. a kind of sodium-ion battery as described in any one of claim 1-7 is with flexible self-supporting electrode material in organic electrolysis The application of sodium ion half-cell is assembled under liquid system.
9. a kind of preparation method of sodium ion half-cell as claimed in claim 8, it is characterised in that:The preparation method includes Following steps:With Ti3C2The Ti prepared with rGO3C2@rGO flexible self-supportings composite material be active material, direct clip size Moderate film makees pole piece with quality;Sodium piece is used as to electrode, and glass fibre membrane (GF/D whatman) is as diaphragm, 1mol/L NaClO4It is dissolved in propene carbonate (PC) and makees electrolyte, be assembled into sodium ion half-cell.
CN201711332068.XA 2017-12-13 2017-12-13 A kind of sodium-ion battery flexible self-supporting electrode material and its application and preparation method Withdrawn CN108183205A (en)

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