CN108461732A - A kind of flexibility sodium metal battery negative material and preparation method thereof - Google Patents

A kind of flexibility sodium metal battery negative material and preparation method thereof Download PDF

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Publication number
CN108461732A
CN108461732A CN201810219406.7A CN201810219406A CN108461732A CN 108461732 A CN108461732 A CN 108461732A CN 201810219406 A CN201810219406 A CN 201810219406A CN 108461732 A CN108461732 A CN 108461732A
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sodium
sodium metal
metal battery
battery
preparation
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谢嫚
周佳辉
陈人杰
吴锋
罗锐
李丽
李月姣
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Beijing Institute of Technology BIT
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Beijing Institute of Technology BIT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • 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
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 present invention relates to a kind of flexible sodium metal battery negative materials and preparation method thereof, belong to sodium metal battery technical field.The material is using graphene aerogel as skeleton, and sodium Metal Distribution is in skeleton structure；The pore diameter range of skeleton is 20~200 μm, and the mass fraction of sodium metal is 90~98% in the material.The preparation method of the material is：Conductive material is added to the water, is then added reducing agent, reaction 6 at 50~200 DEG C~for 24 hours, obtain intermediate product, washing, under 5~10MPa freeze-drying form graphene aerogel, then using graphene aerogel as skeleton at 100~500 DEG C with liquid metal sodium it is compound after obtain.The material possesses good flexible, uniform porosity and bigger serface, and the uniform row core of sodium ion is ensure that as sodium metal battery cathode, alleviates the volume expansion in cyclic process, higher electric conductivity effectively reduces overpotential.

Description

A kind of flexibility sodium metal battery negative material and preparation method thereof
Technical field
The present invention relates to a kind of flexible sodium metal battery negative materials and preparation method thereof, belong to sodium metal battery technology neck Domain.
Background technology
The problems such as Fossil fuel consumption, environmental pollution and global warming, has caused people to cleaning/regenerative resource and electricity The great interest of electrical automobile development.But wind energy, solar energy, some regenerative resources such as tide energy all have unstable and do not connect Continuous feature cannot be effectively applied among actual production, life.In order to solve these problems, advanced energy conversion and Memory technology plays a crucial role.By the unremitting effort of decades, lithium ion battery has become portable electronic device The main power source of part.Since energy density is high, long lifespan, in recent years people increasingly pay close attention to lithium ion battery electric vehicle with Application in terms of extensive energy storage.However lithium resource is limited with respect to reserves, is unevenly distributed, these problems make lithium ion battery into One step develops and large-scale use is restricted.And sodium is a kind of natural energy storage material got a good chance of, sodium and lithium are all the IA major elements have many similarities in terms of physics and chemical property.In addition, seawater be extract sodium it is a kind of almost without The potential resource of limit, and the extractive process of sodium is simple more than lithium.These advantages make storage of the sodium based battery to power grid scale There can be very big attraction.
In the seventies in last century, sulphur sodium (Na-S) battery obtains good hair due to its own abundant resource reserve Exhibition, however, higher operating temperature (270-350 DEG C), expensive electrolyte and additional safety problem have seriously affected Na-S The further research of battery.With the continuous development of sodium-ion battery, by using for reference lithium ion battery liquid electrolyte system, sodium Ion battery anode has been achieved for very big progress.Currently, due to having been applied to commercialized negative electrode of lithium ion battery Graphite can not be applied in sodium ion cathode, and only a small number of negative material such as hard carbons has relatively excellent performance.Another Aspect, sodium metal negative electrode possess very high theoretical capacity (1166mAh/g) and lower oxidation-reduction potential (- 2.714V), Using metallic sodium as cathode, the materials such as sulphur, oxygen are the battery energy storage system of anode with its higher theoretical energy density (sodium sulphur electricity Pond, sodium sky battery, sodium-ion battery), promise to be very much next-generation battery energy storage system.
Although sodium metal negative electrode possesses plurality of advantages, the development of sodium metal negative electrode still suffers from lot of challenges.It is former Because being：Sodium ion is during circulating battery, it is easy to form dendroid branch in interface location due to the uneven of deposition On the one hand crystalline substance may puncture diaphragm and then short circuit causes explosion hazard, on the other hand can also destroy negative with the growth of dendrite The solid electrolyte interface film (SEI films) of pole surface causes exposed metallic sodium to be reacted with electrolyte, consumes the active matter of sodium Matter so that the utilization rate of electrode reduces, and due to the chassis less construction feature of metallic sodium itself, in 100% charge status Under, volume expansion is infinity, seriously destroys the stability of electrode, and SEI films is caused to rupture, and coulombic efficiency reduces, overpotential Increase, at the same time, since sodium metallochemistry stability is poor, in conjunction with can it is relatively low cause can processing difficulties, these problems to sodium gold The commercialization for belonging to cathode proposes huge challenge.In order to solve the dendrite problems of metallic sodium, researcher proposes various solution party Case.Hu liangbing etc. are proposed using technique for atomic layer deposition, grow Al on metallic sodium surface2O3Passivation layer, passivation layer are gathered around Have it is excellent lead ionic nature, mechanical strength and chemical stability, to inhibit the growth of dendrite.Lynden A.Archer Deng using functional ionic additive come the growth of dendrite inhibition, i.e., by metallic sodium surface formed thin film, realize metal The uniform deposition of sodium, and then the growth of dendrite inhibition.The studies above achievement proposes the thinking of many dendrite inhibitions, but is directed to The volume expansion problem that sodium metal negative electrode chassis less construction causes does not obtain effective solution, the propositions such as Hu liangbing Using hard carbon package metals sodium, inhibit the volume expansion in metallic sodium cyclic process, but since hard carbon does not have good flexibility And quality is higher, combination electrode energy density is extremely low.Therefore how to inhibit sodium metal battery cathode dendritic growth while solving body The problem of product expansion, there is very important meaning for the development of the following electrochemical energy storage.
Invention content
In view of this, one of the objects of the present invention is to provide a kind of flexible sodium metal battery negative material, the cathode Material has internal connected mesh skeleton structure.
The second object of the present invention is to provide a kind of preparation method of flexible sodium metal battery negative material, the method It is simple and practicable.
The third object of the present invention is to provide a kind of sodium metal battery, and cell negative electrode material is that one kind of the present invention is soft Property sodium metal battery negative material can inhibit the growth of sodium dendrite in cyclic process under carbonates electrolyte, limit body Product swelling.
To achieve the above object, technical scheme is as follows.
A kind of flexibility sodium metal battery negative material, using graphene aerogel as skeleton, sodium Metal Distribution exists the material In skeleton structure；The pore diameter range of skeleton is 10~50 μm, and the mass fraction of metallic sodium is 90~98% in the material.
A kind of preparation method of flexible sodium metal battery anode material of the present invention, the method step is such as Under：
Conductive material is added to the water, is then added reducing agent, reaction 6 at 50~200 DEG C~for 24 hours, intermediate product is obtained, Washing, under 5~10MPa freeze-drying form graphene aerogel, be then skeleton at 100~500 DEG C using graphene aerogel It is lower to be mixed with liquid metal sodium, obtain a kind of flexible sodium metal negative electrode material；Wherein, the conductive material be carbon black oxide, Graphene oxide, carbon nanotube oxide or hollow carbon balls oxide.
Preferably, the mass ratio of C and O is 1~2.5 in the conductive material:1.
Preferably, reducing agent is one or more of ascorbic acid, ethylenediamine, sodium hydrogensulfite and ammonium chloride.
Preferably, the mass ratio of reducing agent and conductive material is 1~5:1.
Preferably, freeze-drying temperature is -50~-200 DEG C, and the time is 24~48h.
The negative material of a kind of sodium metal battery, the battery is a kind of flexible sodium metal battery cathode of the present invention Material, the battery electrolyte are carbonates electrolyte.
Preferably, the current density of the battery is 0.5mA/cm2~5mA/cm2, the deposition capacity of metallic sodium is 1mAh/ cm2~2mAh/cm2。
Preferably, the battery electrolyte is：By NaClO4The mixing for being dissolved in ethylene carbonate and diethyl carbonate is molten Electrolyte, NaClO are made in liquid4The volume ratio of a concentration of 1.0mol/L, ethylene carbonate and diethyl carbonate is 1：1.
Advantageous effect
A kind of flexible sodium metal battery negative material of the present invention, the material possesses good flexible, uniform Porosity and bigger serface ensure that the uniform row core of sodium ion as sodium metal battery cathode, alleviate in cyclic process Volume expansion, higher electric conductivity effectively reduces overpotential.The material is using Flexible graphene aeroge as skeleton, graphite Alkene aeroge has good mechanical performance and high conductivity, further reduces polarization, it is swollen to limit volume in cyclic process Swollen and dendritic growth problem.Three-dimensional conductive frame contributes to the diffusion of ion, improves security performance and the library of sodium metal negative electrode Human relations efficiency.Due to the machinability of aeroge, it can accurately regulate and control the shape of combination electrode and various dimensions can be processed into Degree.The flexible sodium metallic composite can be one-dimensional, two dimension or three-dimensional.Wherein, one-dimensional is line, and two dimension is face, three-dimensional For cylinder, cuboid, square, circular cone or prism.
A kind of preparation method of flexible sodium metal battery negative material of the present invention, the method is simple and easy to do, leads to Control hydrothermal temperature and time are spent, the uniform intermediate product of pore-size can be obtained, but reaction temperature is not easy more than 200 DEG C, the reaction time is not easy to be more than that for 24 hours, otherwise the functional group of intermediate product disappears totally, and then the electrochemistry for influencing final product is followed Ring performance；The size of aeroge hole can accurately be regulated and controled by being freeze-dried temperature by adjusting, select to have suitable C/O than Graphene oxide presoma can improve the adsorption rate of metallic sodium, and combination electrode, metallic sodium are formed to absorb liquid metal sodium Utilization rate is high, and surfacing is generated without apparent particle.
A kind of sodium metal battery of the present invention reduces effective electricity of electrode surface under carbonates electrolyte Current density to effectively inhibit the growth of sodium dendrite under high current density, while solving the problems, such as volume expansion.
Description of the drawings
Fig. 1 is the scanning electron microscope diagram of graphene aerogel.
Fig. 2 is the X-ray diffractogram of final product made from embodiment 1.
Fig. 3 is the scanning electron microscope diagram of final product made from embodiment 1.
The half-cell that Fig. 4 is assembled by embodiment 8 is in 0.5mA/cm2Current density under deposit 0.5mAh/cm2Metallic sodium Charging and discharging curve.
The half-cell that Fig. 5 is assembled by comparative example 1 is in 0.5mA/cm2Current density under deposit 0.5mAh/cm2Metallic sodium Charging and discharging curve.
The half-cell that Fig. 6 is assembled by embodiment 9 is in 3mA/cm2Current density under deposit 2mAh/cm2Metallic sodium fills Discharge curve.
The half-cell that Fig. 7 is assembled by comparative example 2 is in 3mA/cm2Current density under deposit 2mAh/cm2Metallic sodium fills Discharge curve.
The half-cell that Fig. 8 is assembled by embodiment 10 is in 5mA/cm2Current density under deposit 1mAh/cm2Metallic sodium fills Discharge curve.
The half-cell that Fig. 9 is assembled by comparative example 3 is in 5mA/cm2Current density under deposit 1mAh/cm2Metallic sodium fills Discharge curve.
The charge and discharge for half-cell completely out metallic sodium under the current density of 25mA/g that Figure 10 is assembled by embodiment 11 Electric curve.
Specific implementation mode
With reference to specific embodiment, the present invention is described in further detail.
In following embodiment：
(1) scanning electron microscope (SEM) is tested：
By material cut it is a piece of be sticked on conducting resinl, metal spraying processing after, be sent into sample room carry out material morphology observation.It is used Instrument is field emission scanning electron microscope (FEI, Quanata 200f), accelerating potential 20KV.
(2) X-ray diffraction (XRD) is tested：
Object phase is carried out to material using the Rigaku-D/max-2550pc types x-ray powder diffraction instrument of Hitachi, Japan Analysis, using Cu-k as radiation source, wavelength isUsing Ni filter plates, Guan Liuwei 40mA, pipe pressure is 40KV, is swept Ranging from 10 °~90 ° are retouched, sweep speed is 8 °/min, and step-length is 0.02 °；Material is put into glass slide and is flattened, by glass slide The experimental tank center of embedded x-ray powder diffraction instrument, is tested；The identification of object phase and crystal structure information are soft by JADE5.0 Part is analyzed.
(3) assembling of half-cell：
Using final product made from embodiment 1 as anode and cathode, Whatman glass fibres (GF/D) are diaphragm, by NaClO4It is molten (volume ratio of EC and DEC are 1 to solution in the mixed solution of ethylene carbonate (EC) and diethyl carbonate (DEC)：1) electrolysis is made Liquid, NaClO4A concentration of 1.0mol/L is assembled into CR2032 button cells (half-cell) in argon gas glove box.
(4) charge-discharge performance of the half-cell assembled is tested：
Using Land battery test systems carry out constant current charge-discharge test, setting electric current density, charging/discharging voltage section, The parameters such as circulating cycle number and active matter quality, software records test the charge and discharge curve of battery.
Embodiment 1
A kind of flexibility sodium metal battery cathode material preparation method, steps are as follows for the method：
By the graphene oxide of 40mg (2.5mg/ml), (mass ratio of C and O are 1.95：1) ultrasonic disperse 120min is added The ascorbic acid of 120mg, after stirring 30min, water-bath 6h, obtains intermediate product at 50 DEG C, in being cleaned repeatedly with deionized water Between product, then intermediate product is put into freeze drier, at 10MPa -181 DEG C freeze-drying for 24 hours, obtain graphene gas Graphene aerogel is washed into the disk of Ф=10mm with die punching machine after slice, is transferred in glove box, at 300 DEG C by gel Liquid metal sodium 6mg is adsorbed, a kind of flexible sodium metal battery negative material is obtained.
The results are shown in Figure 1 for the scanning electron microscope of graphene aerogel, and the cavernous structure being stacked with constitutes tightly Close 3d conductive frames, pore-size is at 10 μm or so.
The X ray diffracting spectrum of final product corresponds to Na as shown in Fig. 2, a sharp peak appears in 38 ° or so (110), illustrate that metallic sodium has been adsorbed onto in aeroge skeleton.
The results are shown in Figure 3 for the scanning electron microscope of final product, after graphene aerogel adsorbing metal sodium, the material Piece planar is presented.
After applying certain external force to final product, the shape of script still can be replied, illustrates that final product has good flexibility.
Embodiment 2
A kind of flexibility sodium metal battery cathode material preparation method, steps are as follows for the method：
By the graphene oxide of 40mg (2.5mg/ml), (mass ratio of C and O are 2.5：1) ultrasonic disperse 120min is added The ascorbic acid of 120mg, after stirring 30min, water-bath 6h, obtains intermediate product at 50 DEG C, in being cleaned repeatedly with deionized water Between product, then intermediate product is put into freeze drier, at 10MPa -181 DEG C freeze-drying for 24 hours, obtain graphene gas Graphene aerogel is washed into the disk of Ф=10mm with die punching machine after slice, is transferred in glove box, at 300 DEG C by gel Liquid metal sodium 6mg is adsorbed, a kind of flexible sodium metal battery negative material is obtained.
The scanning electron microscope of graphene aerogel the result shows that, the cavernous structure being stacked with constitutes close 3d Conductive frame, pore-size is at 10 μm or so.
The X ray diffracting spectrum of final product the result shows that, a sharp peak appears in 38 ° or so, corresponds to Na (110), illustrate that metallic sodium has been adsorbed onto in aeroge skeleton.
The scanning electron microscope of final product the result shows that, after graphene aerogel adsorbing metal sodium, the material is presented Piece planar.
After applying certain external force to final product, the shape of script still can be replied, illustrates that final product has good flexibility.
Embodiment 3
A kind of flexibility sodium metal battery cathode material preparation method, steps are as follows for the method：
By the graphene oxide of 40mg (2.5mg/ml), (mass ratio of C and O are 1.95：1) ultrasonic disperse 120min is added The ascorbic acid of 120mg, after stirring 30min, water-bath 6h, obtains intermediate product at 120 DEG C, in being cleaned repeatedly with deionized water Between product, then intermediate product is put into freeze drier, at 10MPa -181 DEG C freeze-drying for 24 hours, obtain graphene gas Graphene aerogel is washed into the disk of Ф=10mm with die punching machine after slice, is transferred in glove box, at 300 DEG C by gel Liquid metal sodium 6mg is adsorbed, a kind of flexible sodium metal battery negative material is obtained.
The scanning electron microscope of graphene aerogel the result shows that, the cavernous structure being stacked with constitutes close 3d Conductive frame, pore-size is at 10 μm or so.
The X ray diffracting spectrum of final product the result shows that, a sharp peak appears in 38 ° or so, corresponds to Na (110), illustrate that metallic sodium has been adsorbed onto in aeroge skeleton.
The scanning electron microscope of final product the result shows that, after graphene aerogel adsorbing metal sodium, the material is presented Piece planar.
After applying certain external force to final product, the shape of script still can be replied, illustrates that final product has good flexibility.
Embodiment 4
A kind of flexibility sodium metal battery cathode material preparation method, steps are as follows for the method：
By the graphene oxide of 40mg (2.5mg/ml), (mass ratio of C and O are 1.95：1) ultrasonic disperse 120min is added The ascorbic acid of 150mg, after stirring 30min, water-bath 6h, obtains intermediate product at 50 DEG C, in being cleaned repeatedly with deionized water Between product, then intermediate product is put into freeze drier, at 10MPa -181 DEG C freeze-drying for 24 hours, obtain graphene gas Graphene aerogel is washed into the disk of Ф=10mm with die punching machine after slice, is transferred in glove box, at 300 DEG C by gel Liquid metal sodium 6mg is adsorbed, a kind of flexible sodium metal battery negative material is obtained.
The scanning electron microscope of graphene aerogel the result shows that, the cavernous structure being stacked with constitutes close 3d Conductive frame, pore-size is at 50 μm or so.
The X ray diffracting spectrum of final product the result shows that, a sharp peak appears in 38 ° or so, corresponds to Na (110), illustrate that metallic sodium has been adsorbed onto in aeroge skeleton.
The scanning electron microscope of final product the result shows that, after graphene aerogel adsorbing metal sodium, the material is presented Piece planar.
After applying certain external force to final product, the shape of script still can be replied, illustrates that final product has good flexibility.
Embodiment 5
A kind of flexibility sodium metal battery cathode material preparation method, steps are as follows for the method：
By the graphene oxide of 40mg (2.5mg/ml), (mass ratio of C and O are 1.95：1) ultrasonic disperse 120min is added The ethylenediamine of 120mg, after stirring 30min, water-bath 6h, obtains intermediate product at 50 DEG C, and centre is cleaned repeatedly with deionized water Then intermediate product is put into freeze drier by product, be freeze-dried for 24 hours for -181 DEG C at 10MPa, obtain graphene airsetting Graphene aerogel is washed into the disk of Ф=10mm with die punching machine after slice, is transferred in glove box, is inhaled at 300 DEG C by glue Attached liquid metal sodium 6mg obtains a kind of flexible sodium metal battery negative material.
The scanning electron microscope of graphene aerogel the result shows that, the cavernous structure being stacked with constitutes close 3d Conductive frame, pore-size is at 10 μm or so.
The X ray diffracting spectrum of final product the result shows that, a sharp peak appears in 38 ° or so, corresponds to Na (110), illustrate that metallic sodium has been adsorbed onto in aeroge skeleton.
The scanning electron microscope of final product the result shows that, after graphene aerogel adsorbing metal sodium, the material is presented Piece planar.
After applying certain external force to final product, the shape of script still can be replied, illustrates that final product has good flexibility.
Embodiment 6
A kind of flexibility sodium metal battery cathode material preparation method, steps are as follows for the method：
By the graphene oxide of 40mg (2.5mg/ml), (mass ratio of C and O are 1.95：1) ultrasonic disperse 120min is added The ascorbic acid of 120mg, after stirring 30min, water-bath 6h, obtains intermediate product at 50 DEG C, in being cleaned repeatedly with deionized water Between product, then intermediate product is put into freeze drier, at 10MPa -181 DEG C freeze-drying for 24 hours, obtain graphene gas Graphene aerogel is washed into the disk of Ф=10mm with die punching machine after slice, is transferred in glove box, at 100 DEG C by gel Liquid metal sodium 6mg is adsorbed, a kind of flexible sodium metal battery negative material is obtained.
The scanning electron microscope of graphene aerogel the result shows that, the cavernous structure being stacked with constitutes close 3d Conductive frame, pore-size is at 30 μm or so.
The X ray diffracting spectrum of final product the result shows that, a sharp peak appears in 38 ° or so, corresponds to Na (110), illustrate that metallic sodium has been adsorbed onto in aeroge skeleton.
The scanning electron microscope of final product the result shows that, after graphene aerogel adsorbing metal sodium, the material is presented Piece planar.
After applying certain external force to final product, the shape of script still can be replied, illustrates that final product has good flexibility.
Embodiment 7
A kind of flexibility sodium metal battery cathode material preparation method, steps are as follows for the method：
By the graphene oxide of 40mg (2.5mg/ml), (mass ratio of C and O are 1.95:1) ultrasonic disperse 120min is added The ascorbic acid of 120mg, after stirring 30min, water-bath 6h, obtains intermediate product at 120 DEG C, in being cleaned repeatedly with deionized water Between product, then intermediate product is put into freeze drier, at 10Mpa -50 DEG C freeze-drying for 24 hours, obtain graphene gas Graphene aerogel is washed into the disk of Ф=10mm with die punching machine after slice, is transferred in glove box, at 300 DEG C by gel Liquid metal sodium 6mg is adsorbed, a kind of flexible sodium metal battery negative material is obtained.
The scanning electron microscope of graphene aerogel the result shows that, the cavernous structure being stacked with constitutes close 3d Conductive frame, pore-size is at 50 μm or so.
The X ray diffracting spectrum of final product the result shows that, a sharp peak appears in 38 ° or so, corresponds to Na (110), illustrate that metallic sodium has been adsorbed onto in aeroge skeleton.
The scanning electron microscope of final product the result shows that, after graphene aerogel adsorbing metal sodium, the material is presented Piece planar.
After applying certain external force to final product, the shape of script still can be replied, illustrates that final product has good flexibility.
Embodiment 8
Using final product made from embodiment 1 as anode and cathode, by NaClO4It is dissolved in ethylene carbonate (EC) and carbonic acid two (volume ratio of EC and DEC are 1 in the mixed solution of ethyl ester (DEC):1) electrolyte, NaClO is made4A concentration of 1.0mol/L, group Dress up half-cell.
Electrochemical property test is carried out to the half-cell assembled：The results are shown in Figure 4, is 0.5mA/ in current density cm2Lower deposition 0.5mAh/cm2Metallic sodium, 350 hours of circulating battery still generate without apparent dendrite, loop cycle performance To stablize, overpotential is maintained at 30mV or so, and the half-cell assembled in cycle initial stage 7-12h, stablize in 30mV or so by overpotential, It is generated without obviously fluctuation, the half-cell of assembling recycles 250-260h, and overpotential is still stablized in 30mV or so.When with test Between growth, overpotential there is no with cycle increase, illustrate that final product made from embodiment 1 effectively inhibits the body of metallic sodium Product expands and improves forming core uniformity.
Comparative example 1
Metallic sodium is washed into the electrode slice of Ф=10mm with die punching machine, while as cathode and anode, by NaClO4Dissolving (volume ratio of EC and DEC are 1 in the mixed solution of ethylene carbonate (EC) and diethyl carbonate (DEC):1) electrolysis is made Liquid, NaClO4A concentration of 1.0mol/L, is assembled into half-cell.
Electrochemical property test is carried out to the half-cell assembled：The results are shown in Figure 5, is 0.5mA/ in current density cm2Lower deposition 0.5mAh/cm2Metallic sodium, polarization potential are 80mV or so.Simultaneously as dendritic growth and volume expansion, assembling Half-cell there is the case where battery short circuit after testing time 255h.The half-cell assembled is in cycle initial stage 7-12h, charge and discharge Electric curve shows apparent spike, this is because dendrite is generated in sodium ion deposition process, as dendritic growth has occurred The rupture of SEI films.The half-cell cycle 250-260h assembled, overpotential rise to 100mV or so, and short circuit occurs in 255h.
Embodiment 9
Using final product made from embodiment 1 as anode and cathode, by NaClO4It is dissolved in ethylene carbonate (EC) and carbonic acid two (volume ratio of EC and DEC are 1 in the mixed solution of ethyl ester (DEC):1) electrolyte, NaClO is made4A concentration of 1.0mol/L, group Dress up half-cell.
Electrochemical property test is carried out to the half-cell assembled：The results are shown in Figure 6, is 3mA/cm in current density2 Lower deposition 2mAh/cm2Metallic sodium, 120 hours of circulating battery still generate without apparent dendrite, and loop cycle performance is steady Fixed, overpotential is maintained at 40mV or so, and the half-cell assembled is in cycle initial stage 5-10h, under larger current density, cathode Overpotential is still stablized in 40mV or so, is generated without obviously fluctuation, and the half-cell of assembling recycles 250-260h, and overpotential is stablized It is maintained at 40mV or so.With the growth of testing time, overpotential illustrates there is no being increased with cycle made from embodiment 1 Final product effectively inhibits the volume expansion of metallic sodium and improves forming core uniformity.
Comparative example 2
Metallic sodium is washed into the electrode slice of Ф=10mm with die punching machine, while as cathode and anode, by NaClO4Dissolving (volume ratio of EC and DEC are 1 in the mixed solution of ethylene carbonate (EC) and diethyl carbonate (DEC):1) electrolysis is made Liquid, NaClO4A concentration of 1.0mol/L, is assembled into half-cell.
Electrochemical property test is carried out to the half-cell assembled：The results are shown in Figure 7, in current density 3mA/cm2Under Deposit 2mAh/cm2Metallic sodium, cycle is highly unstable, is far longer than the polarization potential of cathode in embodiment 3.Simultaneously as branch Crystals growth and volume expansion, the half-cell assembled reach blanking voltage 3.0V after testing time 80h.The half-cell assembled In cycle initial stage 5-10h, charging and discharging curve shows apparent shake, illustrates that the increase with current density, sodium metal are negative The deposition of pole is highly unstable, and Study of Volume Expansion is apparent, and dendritic growth is serious.The half-cell cycle 80-85h assembled, Reach blanking voltage when 82.5h.
Embodiment 10
Using final product made from embodiment 1 as anode and cathode, by NaClO4It is dissolved in ethylene carbonate (EC) and carbonic acid two (volume ratio of EC and DEC are 1 in the mixed solution of ethyl ester (DEC):1) electrolyte, NaClO is made4A concentration of 1.0mol/L, group Dress up half-cell.
Electrochemical property test is carried out to the half-cell assembled：The results are shown in Figure 8, is 5mA/cm in current density2 Lower deposition 1mAh/cm2Metallic sodium, 400 hours of circulating battery still generate without apparent dendrite, and loop cycle performance is steady Fixed, overpotential is maintained at 40mV or so, and the half-cell assembled is in cycle initial stage 20-25h, under larger current density, cathode Overpotential still stablize in 100mV or so, generated without obviously fluctuation.With the growth of testing time, composite negative pole it is whole Body structure is gradually stablized, and final overpotential is maintained at 40mV or so, illustrates final product superhigh specific surface area made from embodiment 1 Feature effectively reduces actual current density, and good mechanical performance inhibits the volume expansion of metallic sodium in cyclic process existing As.
Comparative example 3
Metallic sodium is washed into the electrode slice of Ф=10mm with die punching machine, while as cathode and anode, by NaClO4Dissolving (volume ratio of EC and DEC are 1 in the mixed solution of ethylene carbonate (EC) and diethyl carbonate (DEC):1) electrolysis is made Liquid, NaClO4A concentration of 1.0mol/L, is assembled into half-cell.
As shown in figure 9, being 5mA/cm in current density2It is tested, the charging and discharging curve of the half-cell assembled is as schemed It is shown, in current density 5mA/cm2Lower deposition 1mAh/cm2Metallic sodium, cycle is highly unstable, is far longer than in embodiment 4 and bears The polarization potential of pole.Simultaneously as dendritic growth and volume expansion, the half-cell assembled occurs micro- after testing time 22h Short circuit.The half-cell assembled shows apparent shake, illustrates with electric current in cycle initial stage 20-25h, charging and discharging curve The deposition of the increase of density, sodium metal negative electrode is highly unstable, and dendritic growth is serious.
Embodiment 11
Using final product made from embodiment 1 as anode and cathode, by NaClO4It is dissolved in ethylene carbonate (EC) and carbonic acid two (volume ratio of EC and DEC are 1 in the mixed solution of ethyl ester (DEC):1) electrolyte, NaClO is made4A concentration of 1.0mol/L, group Dress up half-cell.
Electrochemical property test is carried out to the half-cell assembled：As shown in Figure 10, it is filled under the current density of 25mA/g Electricity arrives 1V, and capacity reaches 1064mAh/g, smaller compared to pure sodium metal negative electrode capacitance loss.It illustrates made from embodiment 1 eventually The good flexibility of product ensure that the higher load factor of metallic sodium, improve the mass energy density of material.
It is found by comparing each embodiment, using final product made from embodiment 1 as sodium metal battery negative material, polarization Current potential is low, stable circulation.
Invention include but not limited to above example, it is every carried out under the spirit and principles in the present invention it is any equivalent Replacement or local improvement, all will be regarded as within protection scope of the present invention.

Claims (9)

1. a kind of flexibility sodium metal battery negative material, it is characterised in that：The material is using graphene aerogel as skeleton, sodium gold Category is distributed in skeleton structure；The pore diameter range of skeleton is 10~50 μm, in the material mass fraction of sodium metal be 90~ 98%.
2. a kind of preparation method of flexible sodium metal battery anode material as described in claim 1, it is characterised in that：Institute It is as follows to state method and step：
Conductive material is added to the water, is then added reducing agent, reaction 6 at 50~200 DEG C~for 24 hours, obtain intermediate product, water Wash, under 5~10MPa freeze-drying form graphene aerogel, be then skeleton at 100~500 DEG C using graphene aerogel It is mixed with liquid metal sodium, obtains a kind of flexible sodium metal negative electrode material；Wherein, the conductive material is carbon black oxide, stone Black olefinic oxide, carbon nanotube oxide or hollow carbon balls oxide.
3. a kind of preparation method of flexible sodium metal battery anode material as claimed in claim 2, it is characterised in that：Institute The mass ratio for stating C and O in conductive material is 1~2.5:1.
4. a kind of preparation method of flexible sodium metal battery anode material as claimed in claim 2, it is characterised in that：Also Former agent is one or more of ascorbic acid, ethylenediamine, sodium hydrogensulfite and ammonium chloride.
5. a kind of preparation method of flexible sodium metal battery anode material as claimed in claim 2, it is characterised in that：Also The mass ratio of former agent and conductive material is 1~5:1.
6. a kind of preparation method of flexible sodium metal battery anode material as claimed in claim 2, it is characterised in that：It is cold It is -50~-200 DEG C to freeze drying temperature, and the time is 24~48h.
7. a kind of sodium metal battery, it is characterised in that：The negative material of the battery is a kind of flexible sodium described in claim 1 Metal battery negative material, the battery electrolyte are carbonates electrolyte.
8. a kind of sodium metal battery as claimed in claim 7, it is characterised in that：The current density of the battery is 0.5mA/cm2 ~5mA/cm2, the deposition capacity of sodium metal is 1mAh/cm2~2mAh/cm2。
9. a kind of sodium metal battery as claimed in claim 7, it is characterised in that：The battery electrolyte is：By NaClO4Dissolving Electrolyte, NaClO are made in the mixed solution of ethylene carbonate and diethyl carbonate4A concentration of 1.0mol/L, ethylene carbonate The volume ratio of ester and diethyl carbonate is 1：1.
CN201810219406.7A 2018-03-16 2018-03-16 A kind of flexibility sodium metal battery negative material and preparation method thereof Pending CN108461732A (en)

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CN113764674A (en) * 2020-06-03 2021-12-07 北京理工大学 Electrode carrier loaded with sodium-potassium alloy and preparation method thereof
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CN111952595A (en) * 2020-07-21 2020-11-17 华南理工大学 Dendritic-crystal-free metal negative electrode carrier based on tip effect and preparation method thereof
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Application publication date: 20180828