CN107611348B - flexible electrode material of aluminum ion battery, preparation method of flexible electrode material and aluminum ion battery - Google Patents
flexible electrode material of aluminum ion battery, preparation method of flexible electrode material and aluminum ion battery Download PDFInfo
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Abstract
the invention relates to the field of batteries, and discloses an aluminum ion battery flexible electrode material, a preparation method thereof and an aluminum ion battery, wherein the preparation method of the aluminum ion battery flexible electrode material comprises the following steps: (1) dissolving a carbon-containing polymer in a solvent to obtain a solution; (2) mixing the main body material and/or the precursor of the main body material with the solution to obtain spinning solution, and then performing electrostatic spinning to obtain a spinning substance; (3) optionally pretreating the spinning substance, and then carrying out heat treatment to obtain the flexible electrode material of the aluminum ion battery; the host material contains at least one of a transition metal oxide and a transition metal sulfide. The flexible electrode material for the aluminum ion battery provided by the invention has the advantages of simple preparation method, strong universality and low cost, and the prepared flexible electrode material has higher charge-discharge specific capacity and cycle reversibility when being used for the aluminum ion battery.
Description
Technical Field
The invention relates to the field of batteries, in particular to an aluminum ion battery flexible electrode material, a preparation method thereof and an aluminum ion battery.
background
the flexible energy storage device is a popular direction in current research, and flexible materials are increasingly hot-held due to the advantages of being bendable, convenient to carry and the like, and have huge application prospects, such as curved surface display screens, intelligent clothes, electronic skins, implantable medical devices and the like. Rechargeable aluminum-ion batteries are one of the next generation of intense research devices with high volumetric energy density. As trivalent metal, Al can realize the redox reaction of three electrons, and the alloy has rich reserves and low price, and is a system with great research and development prospects. The common electrode material usually needs a copper foil or an aluminum foil as a current collector, a binder is needed to attach an active material on the current collector, and the electrode material is easy to fall off if being soaked by electrolyte and bent again. The anode, the cathode and the diaphragm of the flexible electrode material are required to be flexible, and the flexible electrode material can be directly used for manufacturing the electrode material. This greatly reduces the overall weight and cost of the battery, and also helps to increase the energy density of the battery, since no additional current collectors, conductive additives, and binders need to be added. Therefore, there is an important research value in developing a flexible aluminum ion battery having high safety, high flexibility and practicality.
In recent years, flexible energy storage devices are arranged in various countries including the united states, japan and korea, and research directions include flexible lithium ion batteries, flexible supercapacitors, flexible sodium ion batteries and corresponding electrolyte systems. Research on flexible electrodes of aluminum ion batteries is just started at present, and finding a simple and efficient method for preparing the flexible electrodes of the aluminum ion batteries is very critical to occupying the field.
In order to solve the above problems, it is important to find a method for effectively improving the conductivity of the electrode material without using a hard current collector. The specific carbon nanofiber framework prepared by the electrostatic spinning method can provide a good conductive network for a main material, so that the carbon nanofiber framework can serve as a current collector. Although there are reports on the preparation of flexible electrodes by electrostatic spinning at home and abroad, for example, in the Nano Lett.2016,16,3321-3328, Liu et al, the preparation of MnFe by electrostatic spinning is adopted2O4the @ C nanofiber flexible electrode is applied to a cathode material of a sodium ion battery, but the flexible material is synthesized by adopting an in-situ chemical method, namely MnFe2O4Is present in the carbon nano-fiber tubes,The structure of the nano-fiber is easy to damage in the high-temperature treatment process, and the synthesis efficiency is low, so that the industrial application is difficult. Xiong et al in Scientific reports 2015,5,9254 also prepared MoS by electrospinning2the/C flexible film is used for a sodium ion battery cathode material, the document adopts Polyacrylonitrile (PAN) as a high polymer to synthesize a one-dimensional carbon nano tube material, the used spinning solvent PAN requires that a solvent is dimethylformamide, the water-insoluble property of the PAN requires that a raw material for preparing a main body material is soluble in the dimethylformamide, so that great limitation is caused to the selection of the raw material, difficulty is caused to the large-scale industrial production, and the MoS flexible film is also synthesized by an in-situ chemical method2present in carbon nano-fibre tubes, also suffer from the above-mentioned drawbacks. N-doped one-dimensional CuCo synthesized by coke Li Fang topic group of southern Kao university by adopting electrostatic spinning method2O4thin film, then used for secondary battery negative electrode material at 1000mA g-1Under the current density of (1), 314mA h g is still obtained after 1000 cycles-1Reversible capacity of (2), even at 5000mA h g-1Still has 296mA h g at high current density-1The reversible capacity of (a). However, the flexible material is synthesized by an in-situ chemical method, CuCo2O4Present in carbon nano-fibre tubes, also suffer from the above-mentioned drawbacks.
Therefore, the method for manufacturing the flexible electrode material of the aluminum ion battery, which is low in cost, high in efficiency and universal, has important research significance.
Disclosure of Invention
The invention aims to overcome the defects that a nanofiber structure in a flexible electrode material is easy to damage, the in-situ synthesis efficiency is low and the conditions are harsh in the prior art, and provides an aluminum ion battery flexible electrode material, a preparation method thereof and an aluminum ion battery.
The inventor of the present invention finds, in the course of research, that, in the prior art, when the flexible electrode is prepared by an electrostatic spinning method, an in-situ chemical synthesis method is mainly used (i.e., raw materials for preparing the flexible electrode material and a spinning solution are mixed together to carry out electrostatic spinning), and the flexible electrode material synthesized by the in-situ chemical synthesis method mainly exists in a carbon tube of a nanofiber, and the flexible electrode material with the structure is easy to damage the structure of the nanofiber in a high-temperature treatment process, and has low synthesis efficiency. In the course of further research, the inventors of the present invention found that, in a flexible electrode material obtained by electrospinning a spinning solution obtained by mixing an aluminum ion battery electrode host material and/or a precursor of the aluminum ion battery electrode host material with a solution (containing a carbon-containing polymer and a solvent), host material particles are distributed among a plurality of carbon nanofibers and do not exist in carbon tubes of the nanofibers. The structure can not damage the nanofiber structure in the high-temperature treatment process, and the electrode assembled by adopting the electrode material can also keep the stability of the carbon nanofiber structure in the de-intercalation process.
Based on the above, the invention provides an aluminum ion battery flexible electrode material, which comprises: a carbon nanofiber network skeleton composed of a plurality of carbon nanofibers, and host material particles distributed among the plurality of carbon nanofibers; the host material particles contain at least one of a transition metal oxide and a transition metal sulfide;
The transition metal oxide is selected from V2O5、VO2、Mn3O4And MoO2At least one of;
the transition metal sulfide is selected from Mo6S8、FeS2、CuS、Ni3S2、TiS2At least one of (1).
The invention provides a preparation method of an aluminum ion battery flexible electrode material, which comprises the following steps:
(1) dissolving a carbon-containing polymer in a solvent to obtain a solution;
(2) Mixing the main body material and/or the precursor of the main body material with the solution to obtain spinning solution, and then performing electrostatic spinning to obtain a spinning substance;
(3) Optionally pretreating the spinning substance, and then carrying out heat treatment to obtain the flexible electrode material of the aluminum ion battery;
The host material contains at least one of a transition metal oxide and a transition metal sulfide;
The transition metal oxide is selected from V2O5、VO2、Mn3O4And MoO2At least one of;
The transition metal sulfide is selected from Mo6S8、FeS2、CuS、Ni3S2、TiS2At least one of (1).
The invention also provides the flexible electrode material of the aluminum ion battery prepared by the method.
The invention also provides an aluminum ion battery, and the electrode material of the aluminum ion battery comprises the electrode material.
the flexible electrode material of the aluminum ion battery provided by the invention has the following advantages:
(1) According to the flexible electrode material prepared by the electrostatic spinning method, the main material particles are distributed among the plurality of carbon nano fibers, the structure is favorable for increasing the conductivity of the main material, and the flexible electrode material is assembled into an aluminum ion battery, so that the transmission of aluminum ions and the infiltration of electrolyte are very favorable;
(2) The flexible electrode material provided by the invention does not need a current collector and a binder, does not need a conductive additive, and can be directly used for assembling an aluminum ion battery;
(3) The flexible electrode material provided by the invention has the characteristic of light weight because a current collector is not needed, can greatly reduce the weight of the battery, improves the energy density of the battery, and has great practical prospect;
(4) The method is characterized in that the main material and/or the precursor of the main material is prepared firstly, and then the main material and/or the precursor is dispersed into the solution to obtain the spinning solution for spinning, and the method is almost suitable for preparing the anode and cathode flexible materials of any aluminum ion battery because the dissolution of the active material is not limited by the spinning solvent;
(5) Compared with the conventional synthetic aluminum ion battery electrode material, the flexible aluminum ion battery electrode material prepared by the electrostatic spinning method can realize the high-rate charge and discharge and long cycle performance of the battery, and has good application value.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
drawings
FIG. 1 is an SEM photograph of a flexible electrode material S1 obtained in example 1 of the present invention;
Fig. 2 is an SEM image of the flexible electrode material D1 prepared in comparative example 1 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
the invention provides an aluminum ion battery flexible electrode material, which comprises the following components: a carbon nanofiber network skeleton composed of a plurality of carbon nanofibers, and host material particles distributed among the plurality of carbon nanofibers; the host material particles contain at least one of a transition metal oxide and a transition metal sulfide;
The transition metal oxide is selected from V2O5、VO2、Mn3O4And MoO2at least one of;
The transition metal sulfide is selected from Mo6S8、FeS2、CuS、Ni3S2、TiS2at least one of (1).
As shown in fig. 1, the particles of the main material in the flexible electrode material for an aluminum ion battery provided by the present invention are distributed among a plurality of carbon nanofibers, whereas in the flexible electrode material provided by the prior art, the particles of the main material are located inside one carbon nanofiber, the particle size of the particles of the main material is limited by the diameter of the carbon nanofiber, and the particle size is smaller, and the flexible electrode material provided by the present invention has no particular limitation on the size of the particles of the main material; in addition, the desorption of ions in the main material particles of the flexible electrode material provided by the prior art can damage the carbon nanofiber structure, and further the overall stability of the flexible electrode material of the aluminum ion battery is influenced.
In order to further improve the electrochemical performance of the flexible electrode material provided by the invention, the average particle size of the host material particles is preferably 20nm to 0.5mm, and more preferably 150nm to 4 μm.
in the invention, the average particle size is counted by a field emission Scanning Electron Microscope (SEM), and is measured by measuring the longest diameter of the main material particles in a shot electron microscope picture, measuring for multiple times and then averaging.
according to the flexible electrode material provided by the invention, the diameter of the carbon nanofiber is preferably 50nm-500nm, more preferably 100nm-500nm, and even more preferably 100nm-250 nm.
The diameter of the carbon nanofiber can be counted by a field emission Scanning Electron Microscope (SEM), and the diameter of the carbon nanofiber can be measured by measuring the maximum diameter of the carbon nanofiber in a shot electron microscope picture, measuring for multiple times and then averaging.
In order to further improve the electrochemical performance of the flexible electrode material, the content of the host material particles is preferably 40 to 90 wt%, the content of the carbon nanofibers is 10 to 60 wt%, the content of the host material particles is more preferably 40 to 80 wt%, the content of the carbon nanofibers is 20 to 60 wt%, the content of the host material particles is more preferably 60 to 80 wt%, and the content of the carbon nanofibers is 20 to 40 wt%.
The contents of the carbon nanofibers and the particles of the main body material in the flexible electrode material can be measured by a thermogravimetric differential thermal (TG-DTA) method, the thermogravimetric differential thermal curve of the flexible electrode material is measured in the air atmosphere, and then the contents of the main body material and the carbon nanofibers are calculated according to the weight loss curve.
The selection range of the types of the main material particles is wide, the main material particles can be various main materials which are conventionally used in the field of aluminum ion batteries, and can be a positive electrode main material or a negative electrode main material. Based on the disclosure of the present specification, those skilled in the art can fully determine which aluminum ion battery electrode host material to use.
according to a preferred embodiment of the present invention, the host material particles contain V2O5、Mn3O4、MoO2、FeS2CuS and Ni3S2At least one of (1).
The thickness of the flexible electrode material for the aluminum ion battery is not particularly limited, and in order to further improve the electrochemical performance of the flexible electrode material for the aluminum ion battery, the thickness of the flexible electrode material for the aluminum ion battery is preferably 0.01 to 5mm, more preferably 0.1 to 3mm, and even more preferably 0.5 to 1 mm.
The invention also provides a preparation method of the flexible electrode material of the aluminum ion battery, which comprises the following steps:
(1) Dissolving a carbon-containing polymer in a solvent to obtain a solution;
(2) Mixing the main body material and/or the precursor of the main body material with the solution to obtain spinning solution, and then performing electrostatic spinning to obtain a spinning substance;
(3) Optionally pretreating the spinning substance, and then carrying out heat treatment to obtain the flexible electrode material of the aluminum ion battery;
The host material contains at least one of a transition metal oxide and a transition metal sulfide;
the transition metal oxide is selected from V2O5、VO2、Mn3O4And MoO2At least one of;
the transition metal sulfide is selected from Mo6S8、FeS2、CuS、Ni3S2、TiS2At least one of (1).
The present invention does not particularly require the mass content of the solvent and the carbon-containing polymer in the solution of step (1) as long as the carbon-containing polymer can be completely dissolved, and preferably, the content of the carbon-containing polymer is preferably 5 to 20% by weight, more preferably 5 to 15% by weight, and still more preferably 7.1 to 11.5% by weight, based on the total weight of the solution.
According to a preferred embodiment of the present invention, the carbonaceous polymer is selected from the group consisting of high polymers having a number average molecular weight of 10000 to 1500000, and more preferably from the group consisting of high polymers having a number average molecular weight of 16000 to 1300000.
In the present invention, as long as a high polymer that can be used for electrospinning can be used in the present invention, the carbon-containing polymer is preferably at least one selected from the group consisting of polyethylene oxide, polyvinylidene fluoride, polymethacrylate, polyethylene oxide, polyvinylpyrrolidone, polyvinylcarbazole, polybenzimidazole, polyethylene terephthalate, polymethyl methacrylate, polystyrene, polyurethane, polyvinyl alcohol, polylactic acid, polyacrylonitrile, and polyvinyl chloride, and more preferably at least one selected from the group consisting of polyacrylonitrile, polyethylene oxide, polyvinylpyrrolidone, and polyvinyl alcohol.
According to the present invention, preferably, the solvent is selected from at least one of dimethylformamide, dimethylacetamide, dimethylsulfoxide, ethylene carbonate, and water.
the solvent of the present invention may be any solvent that can dissolve the carbon-containing compound, and when the carbon-containing compound is a specific substance, those skilled in the art can select an appropriate solvent according to the disclosure of the present specification. The invention will not be described one by one here.
According to the method provided by the present invention, in the step (2), the host material may be mixed with the solution to obtain the spinning solution, and then the spinning solution may be electrostatically spun, or a precursor of the host material may be mixed with the solution to obtain the spinning solution, and then the spinning solution may be electrostatically spun, or the host material and the precursor of the host material may be mixed with the solution to obtain the spinning solution, and then the spinning solution may be electrostatically spun, and the present invention is not particularly limited thereto.
The precursor of the host material according to the present invention is not a raw material for synthesizing the host material, but a substance that has been converted into the host material under the heat treatment conditions described in step (3) by a certain interaction between the raw materials.
According to the method provided by the invention, the selection range of the dosage of the main material and/or the precursor of the main material and the solution is wide, and preferably, the ratio of the mass of the main material and/or the precursor of the main material to the mass of the solution calculated by the carbon-containing polymer is (0.1-2): 1, preferably (0.25-0.6): 1.
When the step (2) is to mix the host material and the precursor of the host material with the solution, the ratio of the mass of the host material and/or the precursor of the host material to the mass of the solution in terms of the carbon-containing polymer means the ratio of the mass of the sum of the host material and the precursor of the host material to the mass of the solution in terms of the carbon-containing polymer.
in the present invention, the particle size of the host material and the precursor of the host material is not particularly limited as long as electrostatic spinning is possible.
according to the method provided by the invention, the particle size of the main material is preferably not more than 1mm, more preferably not more than 0.5mm, and still more preferably 0.15-5 μm.
according to the method provided by the invention, the particle size of the precursor of the host material is preferably not more than 1mm, more preferably not more than 0.5mm, and still more preferably 0.15-5 μm.
In the present invention, the method for obtaining the host material and the precursor of the host material having the above particle size is not particularly limited, and the host material and the precursor of the host material may be ground in at least one step of the production process, or may be ground after the host material and/or the precursor thereof are produced. In addition, certain host materials and/or precursors of host materials may be prepared with products having particle sizes that directly meet the particle size requirements of the present invention for the host materials and/or precursors of host materials, and therefore, may not include a milling process. The person skilled in the art will be able to make a suitable choice as to whether grinding is required and in which particular step grinding is carried out, depending on the different host materials.
According to the method provided by the present invention, the selection of the type of the host material is as described above, and is not described herein again.
the present invention is not particularly limited to the specific embodiment of the mixing in step (2), and preferably, the mixing includes: and (3) contacting the main material and/or the precursor of the main material with the solution, and then sequentially carrying out ultrasonic dispersion and magnetic stirring. The mode of combining ultrasonic dispersion and magnetic stirring is more favorable for dissolving the main body material and/or the precursor of the main body material, and further more favorable for improving the electrochemical performance of the flexible electrode material of the aluminum ion battery.
According to the method provided by the invention, the ultrasonic dispersion can be carried out according to the conventional technical means in the field, and preferably, the frequency of the ultrasonic dispersion is 40kHz-100kHz, and the time is 0.5-6 h.
According to the method provided by the invention, the magnetic stirring can be carried out according to the conventional technical means in the field, preferably, the rotating speed of the magnetic stirring is 150rpm-1000rpm, and the time is 1-20h, and further preferably, the rotating speed of the magnetic stirring is 400rpm-600rpm, and the time is 4-10 h.
According to a preferred embodiment of the present invention, the conditions of the electrospinning include: the voltage is 10kV-30kV, and more preferably 15kV-22 kV; the distance between the filament outlet and the receiver is 10cm-25cm, and the preferred distance is 15cm-20 cm; the advancing speed is 0.01mm/min-0.5mm/min, and more preferably 0.08mm/min-0.2 mm/min.
According to the method provided by the invention, the spinning substance can be obtained by stripping the product obtained in the step (2) from a receiver (which can be aluminum foil).
According to the method provided by the invention, preferably, the pretreatment conditions comprise: the temperature is 100-500 deg.C, preferably 250-350 deg.C, more preferably 250-300 deg.C, and the time is 30-300min, preferably 120-300min, more preferably 120-180 min.
according to the method provided by the present invention, preferably, the heat treatment conditions include: under inert atmosphere, the temperature is 300-1600 ℃, more preferably 450-900 ℃, more preferably 450-600 ℃, and the time is 1-12h, more preferably 4-10 h.
The inert atmosphere is not particularly limited in the present invention, and may be provided by one or more of nitrogen, helium, argon and neon, and preferably argon.
The invention also provides the flexible electrode material of the aluminum ion battery prepared by the method.
The invention also provides an aluminum ion battery, wherein the electrode material of the aluminum ion battery comprises the electrode material.
According to the present invention, the aluminum ion battery may be a full battery or a half battery. When the electrode material is used for testing the electrical property of the battery electrode material, a half battery is adopted for testing. The half-cell may further include a counter electrode, a separator, and an electrolyte. Wherein, the counter electrode is a metal aluminum sheet. The diaphragm is used for avoiding the short circuit of the battery caused by the direct contact of the positive electrode and the negative electrode, and for example, glass fiber Whatman GF/C No.1822-047 can be adopted. Wherein, the electrolyte can be an ionic liquid electrolyte conventionally used in the field, for example, an ionic liquid of aluminum chloride and imidazole halide (preferably, the molar ratio of the aluminum chloride to the imidazole halide is 1.1-1.5: 1) is an electrolyte.
the aluminum ion battery can be assembled in the form of a button cell in a glove box filled with inert gas.
by adopting the flexible electrode material, the aluminum ion battery with higher reversible discharge specific capacity and better stability can be obtained, and a current collector, a conductive additive and a binder are not needed.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the electrospinning apparatus was purchased from the national institute of science and technology development, GmbH, Yongkang, Beijing, under the type Elite series;
SEM analysis was performed using a field emission scanning electron microscope (model S-4800, available from Hitachi, Japan);
Assembling the battery by adopting a Michelonan argon protection glove box;
The magnetic stirrer is a German IKA topolinio magnetic stirrer;
the membrane is glass fiber Whatman GF/C NO. 1822-047;
the diameter of the carbon nanofiber is counted by adopting a field emission Scanning Electron Microscope (SEM), and is measured by measuring the maximum diameter of the carbon nanofiber in a shot electron microscope picture, measuring for multiple times and then taking an average value.
The average particle size of the main material particles is counted by a field emission Scanning Electron Microscope (SEM), and is measured by measuring the longest diameter of the main material particles in a shot electron microscope picture, measuring for multiple times and then taking an average value;
In the flexible electrode material, the contents of carbon nanofibers and particles of a main body material are measured by adopting a thermogravimetric differential thermal (TG-DTA) method, a thermogravimetric differential thermal curve of the flexible electrode material is measured in the air atmosphere, and then the contents of the main body material and the carbon nanofibers are calculated according to a weight loss curve.
Example 1
transition metal oxide MoO2And preparing the flexible electrode material.
(1) 6.5g of ammonium molybdate tetrahydrate (NH) are weighed4)6Mo7O24·4H2O (commercially available from acros, Inc. under the designation 205851000) was ground in an agate mortar for 30min, and the resulting powder was calcined in an air muffle furnace at 300 ℃ for 30min and then in an argon tube furnace at 600 ℃ for 5h to give MoO2powder (particle size about 4.3 μm);
(2) weighing 2g of polyethylene oxide (PEO, with a number average molecular weight of 600000, the same below) and dissolving in deionized water, stirring to form a solution with a mass content of 11.5 wt%;
(3) weighing 0.5g of MoO obtained in step (1)2Adding the powder into the solution in the step (2), stirring uniformly, and then sequentially performing ultrasonic dispersion (100 kH)z, 2h) and magnetic stirring (700rpm, 8h) to obtain a spinning solution, putting the obtained spinning solution into a 10ml disposable injector, putting the injector into an electrostatic spinning instrument for electrostatic spinning, winding a circle of aluminum foil on a receiving roller to receive the nano-fibers obtained by spinning, wherein the electrostatic spinning conditions comprise that: the advancing speed is 0.08mm/min, the distance between a filament outlet (needle head) and a receiver (receiving roller) is 18cm, the spinning voltage is 20kV, the obtained spinning material is taken off from the aluminum foil, the pretreatment is carried out for 2h at 300 ℃ in a muffle furnace, and then the heat treatment is carried out for 5h at 600 ℃ in a tube furnace under the argon atmosphere, thus obtaining the flexible electrode material S1. The thickness of the prepared flexible electrode material S1 was 1.5 mm.
SEM analysis of the Flexible electrode Material S1, MoO as shown in FIG. 12the particles are distributed among the plurality of carbon nanofibers.
The diameter of the carbon nanofibers of the flexible electrode material S1, the average particle diameter of the host material particles, and the contents of the carbon nanofibers and the host material particles were analyzed, and the results are listed in table 1.
comparative example 1
6.5g of ammonium molybdate tetrahydrate (NH) are weighed4)6Mo7O24·4H2And grinding O in an agate mortar for 30min, weighing 2g of PEO, mixing the PEO and the PEO, dissolving the PEO and the PEO in deionized water, and stirring to form a spinning solution with the mass content of the PEO of 11.5 wt%. Then, the same electrospinning, pretreatment and heat treatment as in example 1 were carried out to obtain a flexible electrode material D1.
SEM analysis of the flexible electrode material D1 is carried out, and the obtained SEM image is shown in FIG. 2, and from the SEM image, MoO as the main material can be seen in FIG. 22The particles are positioned inside the carbon tube of the carbon nano fiber and present a one-dimensional structure.
The diameter of the carbon nanofibers of the flexible electrode material D1, the average particle size of the host material particles, and the contents of the carbon nanofibers and the host material particles were analyzed, and the results are shown in table 1, and since the particle size of the host material particles is limited to the carbon nanofibers, the particle size of the host material particles is significantly smaller than that of the flexible electrode material S1 obtained in example 1.
example 2
Oxidation of transition metalsThing V2O5and preparing the flexible electrode material.
(1) 1.456g of V2O5mixing the powder (purchased from Sigma) with 60mL of deionized water, magnetically stirring at room temperature (400rpm) for 30min, then adding 10mL of 30% hydrogen peroxide by volume fraction into the solution, and continuously stirring for 30min to obtain a uniform and transparent orange solution;
(2) Transferring the orange solution obtained in the step (1) to a 100mL reaction kettle, then carrying out heat preservation and heating at 200 ℃ for 96h, respectively washing the obtained precipitate with deionized water and ethanol for 3 times after cooling to room temperature (25 ℃), and carrying out vacuum drying at 90 ℃ for 12h to obtain V2O5Precursor powder (particle size about 180 nm);
(3) Weighing 1g of polyacrylonitrile (PAN, the number average molecular weight of 150000, the same below) powder, dissolving in Dimethylformamide (DMF), and stirring to form a solution with a mass content of 7.1 wt%;
(4) Weighing 0.6g of V obtained in step (2)2O5Adding precursor powder into the solution obtained in the step (3), uniformly stirring, then sequentially performing ultrasonic dispersion (40kHz, 2 hours) and magnetic stirring (1000rpm, 20 hours) to obtain a spinning solution, filling the obtained spinning solution into a 10ml disposable injector, putting the injector into an electrostatic spinning instrument for electrostatic spinning, winding a circle of aluminum foil on a receiving roller to receive the nano-fibers obtained by spinning, wherein the electrostatic spinning conditions comprise: the advancing speed is 0.08mm/min, the distance between a filament outlet (needle head) and a receiver (receiving roller) is 15cm, the spinning voltage is 15kV, the obtained spinning material is taken off from an aluminum foil, the pretreatment is carried out for 2h at 280 ℃ in a muffle furnace, and then the heat treatment is carried out for 4h at 500 ℃ in the argon atmosphere, thus obtaining the flexible electrode material S2. The thickness of the prepared flexible electrode material S2 was 1 mm.
SEM analysis of the flexible electrode material S2 shows that V2O5the particles are distributed among the plurality of carbon nanofibers.
The diameter of the carbon nanofibers of the flexible electrode material S2, the average particle diameter of the host material particles, and the contents of the carbon nanofibers and the host material particles were analyzed, and the results are listed in table 1.
Example 3
Transition metal oxide Mn3O4and preparing the flexible electrode material.
(1) Weighing 4.41g of tetrahydrate manganese acetate, dissolving in 150mL of deionized water, and uniformly stirring until the manganese acetate is completely dissolved to obtain a solution A;
(2) Dissolving 2mL of hydrazine hydrate with the mass content of 98% in 120mL of deionized water, and uniformly stirring to obtain a hydrazine hydrate solution B; then, pumping the solution A and the solution B into the same reactor by using a peristaltic pump, stirring for 12 hours at room temperature by using a magnetic stirrer at the stirring speed of 400rpm, and then standing and aging for 12 hours at 25 ℃; filtering the aged mixture, washing the precipitate with deionized water for 3 times, and drying the precipitate in an oven at 80 deg.C in air atmosphere for 24 hr to obtain Mn3O4Precursor powder (particle size about 3 μm);
(3) Weighing 2g of polyvinylpyrrolidone (PVP, with the number average molecular weight of 1300000, the same below) powder, dissolving in distilled water, and stirring to form a solution with the mass content of 10 wt%;
(4) weighing 1g of Mn obtained in the step (2)3O4Precursor powder is added into the solution obtained in the step (3), the solution is uniformly stirred, then ultrasonic dispersion (100kHz, 2 hours) and magnetic stirring (500rpm, 10 hours) are sequentially carried out to obtain spinning solution, the obtained spinning solution is filled into a 10ml disposable injector and is put into an electrostatic spinning instrument for electrostatic spinning, a circle of aluminum foil is wound on a receiving roller to receive the nano-fibers obtained by spinning, and the electrostatic spinning conditions comprise that: the advancing speed is 0.2mm/min, the distance between a filament outlet (needle head) and a receiver (receiving roller) is 20cm, the spinning voltage is 20kV, the obtained spinning material is taken off from the aluminum foil, the pretreatment is carried out for 3h at 250 ℃ in a muffle furnace, and then the heat treatment is carried out for 10h at 450 ℃ in the argon atmosphere, thus obtaining the flexible electrode material S3. The thickness of the prepared flexible electrode material S3 was 1 mm.
SEM analysis is carried out on the flexible electrode material S3, and the SEM analysis result shows that Mn is contained3O4The particles are distributed among the plurality of carbon nanofibers.
The diameter of the carbon nanofibers of the flexible electrode material S3, the average particle diameter of the host material particles, and the contents of the carbon nanofibers and the host material particles were analyzed, and the results are listed in table 1.
example 4
Transition metal sulfide FeS2And preparing the flexible electrode material.
(1) 2g of FeS are weighed2Powder (99.9%, available from Alfa Aesar) was placed in a ball mill pot, appropriate amount of milling balls (keeping the weight ratio of balls to powder at 10: 1) was added, the ball mill pot was flushed with argon and ball milled at 500rpm for 24h to obtain FeS2Powder (particle size about 200 nm);
(2) weighing 1.5g of PAN, dissolving in DMF solution, and stirring to form a solution with the mass content of 10 wt%;
(3) Weighing 0.8g of FeS obtained in the step (1)2Adding powder into the solution obtained in the step (2), uniformly stirring, then sequentially performing ultrasonic dispersion (50kHz, 2h) and magnetic stirring (400rpm, 10h) to obtain a spinning solution, filling the obtained spinning solution into a 10ml disposable syringe, putting the syringe into an electrostatic spinning instrument for electrostatic spinning, winding a circle of aluminum foil on a receiving roller to receive the nanofibers obtained by spinning, wherein the electrostatic spinning conditions comprise that: the advancing speed is 0.05mm/min, the distance between a filament outlet (needle head) and a receiver (receiving roller) is 20cm, the spinning voltage is 16kV, the obtained spinning material is peeled off from the aluminum foil, and then the heat treatment is carried out for 4 hours at the temperature of 500 ℃ in the argon atmosphere, so that the flexible electrode material S4 is obtained. The thickness of the prepared flexible electrode material S4 was 1.5 mm.
SEM analysis is carried out on the flexible electrode material S4, and the result of the SEM analysis shows that FeS2the particles are distributed among the plurality of carbon nanofibers.
The diameter of the carbon nanofibers of the flexible electrode material S4, the average particle diameter of the host material particles, and the contents of the carbon nanofibers and the host material particles were analyzed, and the results are listed in table 1.
Example 5
And (3) preparing a transition metal sulfide CuS flexible electrode material.
(1) 2g of CuCl are weighed out2·2H2O was mixed with 40mL of ethylene glycol and then heated to 120 ℃ with stirring and recorded as a solutiona; 3.6g of (NH) are weighed2)2CS is mixed with 40mL of glycol and is marked as solution B; mixing the solution A and the solution B, transferring the mixture into a 100mL reaction kettle after magnetic stirring (400rmp) for 30min, heating the obtained mixed solution at 140 ℃ for 90min, cooling to room temperature, washing the obtained precipitate with deionized water and ethanol for three times respectively, and then drying in vacuum at 60 ℃ for 12h to obtain CuS powder (the particle size is about 3.2 mu m);
(2) weighing 1g of PAN powder, dissolving the PAN powder in a DMF solution, and stirring to form a solution with the mass content of 8.3 wt%;
(3) weighing 0.5g of CuS powder obtained in the step (1), adding the CuS powder into the solution obtained in the step (2), uniformly stirring, sequentially performing ultrasonic dispersion (100kHz, 2h) and magnetic stirring (600rpm and 10h) to obtain a spinning solution, filling the obtained spinning solution into a 10ml disposable injector, putting the injector into an electrostatic spinning instrument for electrostatic spinning, winding a circle of aluminum foil on a receiving roller to receive nano fibers obtained by spinning, wherein the electrostatic spinning conditions comprise that: the advancing speed is 0.1mm/min, the distance between a filament outlet (needle head) and a receiver (receiving roller) is 15cm, the spinning voltage is 22kV, the obtained spinning material is taken off from an aluminum foil, the pretreatment is carried out for 2h at 250 ℃ in a muffle furnace, and then the heat treatment is carried out for 5h at 500 ℃ in a tube furnace in argon atmosphere, thus obtaining the flexible electrode material S5. The thickness of the prepared flexible electrode material S5 was 2 mm.
SEM analysis of the flexible electrode material S5 showed that CuS particles were distributed among the plurality of carbon nanofibers.
The diameter of the carbon nanofibers of the flexible electrode material S5, the average particle diameter of the host material particles, and the contents of the carbon nanofibers and the host material particles were analyzed, and the results are listed in table 1.
example 6
Transition metal sulfide Ni3S2And preparing the flexible electrode material.
(1) 1.5g of Ni were weighed3S2Putting appropriate amount of grinding balls (keeping the weight ratio of the balls to the powder at 10: 1) into a ball milling tank filled with argon, and ball milling at 500rpm for 24h to obtain the final product (obtained from alfa corporation under the reference 035661)To Ni3S2Powder (particle size about 1.3 μm);
(2) Weighing 2g of polyvinyl alcohol (PVA, the number average molecular weight is 20000) and dissolving in deionized water, and stirring to form a solution with the mass content of 10 wt%;
(3) Weighing 1g of micron-sized Ni obtained in the step (1)3S2Adding powder into the solution obtained in the step (2), uniformly stirring, then sequentially performing ultrasonic dispersion (100kHz, 2h) and magnetic stirring (600rpm, 10h) to obtain a spinning solution, filling the obtained spinning solution into a 10ml disposable syringe, putting the syringe into an electrostatic spinning instrument for electrostatic spinning, winding a circle of aluminum foil on a receiving roller to receive the nanofibers obtained by spinning, wherein the electrostatic spinning conditions comprise that: the advancing speed is 0.1mm/min, the distance between a filament outlet (needle head) and a receiver (receiving roller) is 15cm, the spinning voltage is 22kV, the obtained spinning material is taken off from an aluminum foil, the pretreatment is carried out for 2 hours at 280 ℃ in a muffle furnace, and then the heat treatment is carried out for 4 hours at 500 ℃ in a tube furnace in argon atmosphere, thus obtaining the flexible electrode material S6. The thickness of the prepared flexible electrode material S6 was 2 mm.
SEM analysis is carried out on the flexible electrode material S6, and the SEM analysis result shows that Ni is contained in the flexible electrode material3S2The particles are distributed among the plurality of carbon nanofibers.
The diameter of the carbon nanofibers of the flexible electrode material S6, the average particle diameter of the host material particles, and the contents of the carbon nanofibers and the host material particles were analyzed, and the results are listed in table 1.
TABLE 1
test example 1
Electrochemical performance tests were performed on the flexible battery materials obtained in examples 1 to 6 and comparative example 1. Specifically, the method comprises the following steps:
The flexible battery materials obtained in the examples 1 to 6 and the comparative example 1 are assembled into an aluminum ion battery, a metal aluminum sheet is used as a counter electrode, glass fiber Whatman GF/C NO.1822-047 is used as a diaphragm, ionic liquid of aluminum chloride and halogenated imidazole (the molar ratio of the aluminum chloride to the halogenated imidazole is 1.3: 1) is used as electrolyte, a button cell (CR2025) is assembled in an argon glove box, and the flexible battery materials are placed for 24 hours and then subjected to charge and discharge tests on a LAND 2001 CT2001A tester. The results are shown in Table 2.
TABLE 2
As can be seen from table 2, aluminum ions assembled with the flexible electrode materials prepared in examples 1 to 6 can realize reversible charge and discharge with high specific capacity, and have good cycling stability. In addition, the flexible electrode material provided by the invention does not need a current collector and a binder, does not need a conductive additive, and can be directly used for assembling the aluminum ion battery. As can be seen from comparison of the results of example 1 and comparative example 1, the particle size of the flexible electrode material provided by the present invention is not limited by the carbon nanofibers, and the flexible electrode material can exhibit more excellent electrochemical cycling stability.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (21)
1. An aluminum-ion battery comprising a flexible electrode material comprising: a carbon nanofiber network skeleton composed of a plurality of carbon nanofibers, and host material particles distributed among the plurality of carbon nanofibers; the flexible electrode material does not need a current collector, a binder and a conductive additive, and is directly used for assembling the lithium ion battery; the host material particles contain at least one of a transition metal oxide and a transition metal sulfide;
The transition metal oxideis selected from V2O5、VO2And Mn3O4At least one of;
The transition metal sulfide is selected from Mo6S8、FeS2、CuS、Ni3S2、TiS2At least one of;
The content of the main body material particles is 40-80 wt%, and the content of the carbon nano-fibers is 20-60 wt%;
The average particle size of the main material particles is 1-4 μm;
the diameter of the carbon nanofiber is 50nm-500 nm;
The thickness of the flexible electrode material of the aluminum ion battery is 0.01-5 mm;
the preparation method of the flexible electrode material comprises the following steps:
(1) Dissolving a carbon-containing polymer in a solvent to obtain a solution;
(2) Mixing the main body material and/or the precursor of the main body material with the solution to obtain spinning solution, and then performing electrostatic spinning to obtain a spinning substance;
(3) Optionally pretreating the spinning substance, and then carrying out heat treatment to obtain the flexible electrode material of the aluminum ion battery;
The precursor of the host material does not refer to a raw material for synthesizing the host material, but is a substance which has generated a certain interaction with each other and can be converted into the host material under the heat treatment condition in the step (3).
2. the aluminum-ion battery of claim 1, wherein the carbon nanofibers have a diameter of 100nm-250 nm.
3. The aluminum-ion battery of claim 1,
the particles of the host material contain V2O5、Mn3O4、FeS2CuS and Ni3S2At least one of (1).
4. A method of making the aluminum-ion battery of claim 1, the aluminum-ion battery comprising a flexible electrode material, the method comprising:
(1) Dissolving a carbon-containing polymer in a solvent to obtain a solution;
(2) Mixing the main body material and/or the precursor of the main body material with the solution to obtain spinning solution, and then performing electrostatic spinning to obtain a spinning substance, wherein the particle size of the main body material is 0.15-5 mu m, and the particle size of the precursor of the main body material is 0.15-5 mu m;
(3) and optionally pretreating the spinning material, and then carrying out heat treatment to obtain the flexible electrode material of the aluminum ion battery.
5. The method according to claim 4, wherein the carbon-containing polymer is contained in an amount of 5 to 20 wt% based on the total weight of the solution.
6. The method according to claim 4, wherein the carbon-containing polymer is contained in an amount of 5 to 15 wt% based on the total weight of the solution.
7. The method according to claim 4, wherein the carbon-containing polymer is contained in an amount of 7.1 to 11.5 wt% based on the total weight of the solution.
8. The production method according to claim 4,
the carbon-containing polymer is at least one selected from polyethylene oxide, polyvinylidene fluoride, polymethacrylate, polyethylene oxide, polyvinylpyrrolidone, polyvinyl carbazole, polybenzimidazole, polyethylene terephthalate, polymethyl methacrylate, polystyrene, polyurethane, polyvinyl alcohol, polylactic acid, polyacrylonitrile and polyvinyl chloride.
9. the production method according to claim 4, wherein the carbon-containing polymer is at least one of polyacrylonitrile, polyethylene oxide, polyvinylpyrrolidone, and polyvinyl alcohol.
10. the production method according to claim 4, wherein the solvent is selected from at least one of dimethylformamide, dimethylacetamide, dimethylsulfoxide, ethylene carbonate, and water.
11. the production method according to any one of claims 4 to 10, wherein a ratio of a mass of the host material and/or a precursor of the host material to a mass of the solution in terms of the carbon-containing polymer is (0.1 to 2): 1.
12. The production method according to claim 11, wherein a ratio of a mass of the host material and/or a precursor of the host material to a mass of the solution in terms of the carbon-containing polymer is (0.25-0.6): 1.
13. the production method according to any one of claims 4 to 10,
the host material contains V2O5、Mn3O4、FeS2CuS and Ni3S2at least one of (1).
14. the production method according to any one of claims 4 to 10,
in step (2), the mixing process comprises: and (3) contacting the main body material and/or the precursor of the main body material with the solution, and then sequentially carrying out ultrasonic dispersion and magnetic stirring.
15. The production method according to claim 14,
The frequency of the ultrasonic dispersion is 40kHz-100kHz, and the time is 0.5-6 h;
The rotation speed of the magnetic stirring is 150rpm-1000rpm, and the time is 1-20 h.
16. The production method according to any one of claims 4 to 10,
The electrostatic spinning conditions include: the voltage is 10kV-30 kV; the distance between the filament outlet and the receiver is 10cm-25 cm; the advancing speed is 0.01mm/min-0.5 mm/min.
17. The production method according to any one of claims 4 to 10,
The electrostatic spinning conditions include: the voltage is 15kV-22 kV; the distance between the filament outlet and the receiver is 15cm-20 cm; the advancing speed is 0.08mm/min-0.2 mm/min.
18. The production method according to any one of claims 4 to 10,
The pretreatment conditions include: the temperature is 100-500 deg.C, and the time is 30-300 min.
19. The production method according to claim 18, wherein the conditions of the pretreatment include: the temperature is 250-350 deg.C, and the time is 120-300 min.
20. the production method according to any one of claims 4 to 10,
The conditions of the heat treatment include: under inert atmosphere, the temperature is 300-1600 ℃, and the time is 1-12 h.
21. the production method according to claim 20, wherein,
The conditions of the heat treatment include: the reaction is carried out under the inert atmosphere, the temperature is 450-900 ℃, and the time is 2-12 h.
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