CN113793980A - Rechargeable organic calcium ion battery and preparation method thereof - Google Patents
Rechargeable organic calcium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention provides a rechargeable organic calcium ion battery and a preparation method thereof, wherein the rechargeable organic calcium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the diaphragm and the electrolyte are arranged between the positive plate and the negative plate; the positive active material of the positive plate is a layered vanadium oxide which can allow cations forming calcium salt to be reversibly inserted and removed; the negative plate comprises activated carbon cloth or metal calcium; the electrolyte comprises an electrolyte calcium salt, an organic solvent and/or an ionic liquid. The rechargeable organic calcium ion battery provided by the invention has excellent cycle stability and long service life, is a potential application material of a high-power and long-service-life calcium ion battery, and has wide application prospect in the aspect of large-scale energy storage.
Description
Technical Field
The invention relates to the technical field of novel chemical power sources and new energy materials, in particular to a rechargeable organic calcium ion battery and a preparation method thereof.
Background
Calcium ion batteries have gained increased attention in recent years as an energy storage technology that potentially replaces lithium ion batteries. The working principle of the calcium ion battery is similar to that of the lithium ion battery, but the storage and release of the charge in the battery are realized through the migration of calcium ions. And a positive electrode material achieving high capacity, long cycle life and appropriate voltage is very important for the research and development of calcium batteries. Estimated according to Dompablo and colleagues, with 200mA h g-1A reversible capacity of 2.5V and an operating potential of 2.5V will result in a higher energy density for calcium metal batteries than the best lithium ion batteries at present. To achieve this goal, we focus on nanostructured double-layer vanadium oxide positive electrode materials. This material exhibits a double-layer structure with large interlayer spacing and crystal water in the middle layer. These structural features make it well suited for intercalation/deintercalation of multivalent ions and have high capacity. It has been demonstrated that vanadium oxide with a bilayer structure shows more than 300mA hr g in a zinc ion battery-1High capacity of (2). Therefore, we consider the double-layer vanadium oxide to be a high-capacity positive electrode for calcium storage, and hopefully achieve higher capacity.
However, previous studies have shown that the original bilayer V2O5·nH2O generally suffers from severe structural degradation and collapse during ion intercalation/deintercalation, which results in rapid capacity fade. In this connection, the metal ion pre-intercalates the derivative (A)xV2O5·nH2O, a corresponds to a metal ion) is considered a promising candidate because the pre-intercalation strategy has proven to be an effective method to enhance the structural stability of the layered positive electrode. For example, Zn is reportedxV2O5·H2O and CaxV2O5·H2O has high capacity and stable Zn2+Storage capacity.
Based on the above-mentioned idea, the development of a high capacity and high stability calcium battery positive electrode based on a double-layer vanadium oxide is a very challenging issue.
Disclosure of Invention
In view of the above, the present invention provides a rechargeable organic calcium-ion battery and a method for manufacturing the same, in which the calcium-ion battery uses a layered vanadium oxide as an electrode active material to achieve high energy density and long cycle life.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a rechargeable organic calcium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the diaphragm and the electrolyte are arranged between the positive plate and the negative plate;
the positive plate comprises a positive current collector and a positive material, wherein the positive material comprises a positive active material, and the positive active material is a layered vanadium oxide capable of allowing cations forming calcium salt to be reversibly embedded and removed;
the negative plate comprises activated carbon cloth or metal calcium, and both the activated carbon cloth or the metal calcium can be used as a negative current collector and a negative active material;
the electrolyte comprises an electrolyte calcium salt, an organic solvent and/or an ionic liquid.
Optionally, the vanadium oxide has the formula MxVyOz·nH2O, wherein M is a metal ion and comprises one of magnesium, calcium or strontium; x is in the range of 0<x<0.5, y is in the range of 0<y<20, z is in the range of 0<z<20, n is in the range of 0<n<2。
Optionally, the membrane comprises one of a fiberglass membrane, a polytetrafluoroethylene membrane, and filter paper.
Optionally, the electrolyte calcium salt comprises calcium hexafluorophosphate or calcium bistrifluoromethylsulfonimide.
Optionally, the concentration of the electrolyte is in the range of 0.1mol/L to 1.0 mol/L.
Another object of the present invention is to provide a method for preparing a rechargeable organic calcium ion battery, which is used for preparing the rechargeable organic calcium ion battery, and comprises the following steps:
s1, preparing a positive plate: mixing vanadium oxide, a conductive agent and a binder into slurry according to a certain proportion to prepare a positive electrode material, uniformly coating the positive electrode material on the surface of a positive electrode current collector, drying and cutting to obtain the positive electrode plate;
s2, preparing a negative plate: performing surface treatment on metallic calcium or activated carbon cloth to obtain the negative plate;
s3, preparing electrolyte: adding electrolyte calcium salt into an organic solvent and/or ionic liquid, and stirring and mixing to obtain the electrolyte;
s4, preparing a diaphragm: cutting a glass fiber diaphragm, a polytetrafluoroethylene diaphragm or filter paper into required sizes, and drying to obtain the diaphragm;
and S5, tightly stacking the positive plate, the diaphragm and the negative plate in sequence, adding the electrolyte to completely infiltrate the diaphragm, and then packaging the stacked part into a battery shell to obtain the rechargeable organic calcium ion battery.
Optionally, in step S1, the positive electrode current collector includes one of a copper foil, an aluminum foil, a titanium foil, a molybdenum foil, a nickel foam and a stainless steel foil, the conductive agent includes one of acetylene black, ketjen black, activated carbon, carbon fiber and graphite carbon nanotube, and the binder includes one of polyvinylidene fluoride, sodium carboxymethyl cellulose and polytetrafluoroethylene.
Optionally, the positive electrode material comprises 60-90% of the vanadium oxide, 5-30% of the conductive agent and 5-10% of the binder in percentage by weight.
Optionally, the coating thickness of the cathode material on the surface of the cathode current collector in step S1 is in the range of 60 μm to 200 μm.
Alternatively, the surface treatment in step S2 includes washing with ethanol, isopropanol, or water, and then drying.
Compared with the prior art, the rechargeable organic calcium ion battery and the preparation method thereof provided by the invention have the following advantages:
(1) the rechargeable organic calcium ion battery prepared by the invention has excellent cycle stability and long service life by utilizing the mechanism that calcium ions can reversibly perform de-intercalation energy storage in vanadate materials in organic electrolyte, and has wide application prospect in large-scale energy storage.
(2) The preparation method has low requirement on equipment, simple and feasible process, short operation period and easy expanded production, the electrolyte adopts organic calcium ion electrolyte, and the cathode adopts carbon cloth or metal calcium material with rich resources and low price; the method has the characteristics of strong universality, simple process, programmable process and excellent electrochemical performance of the obtained material, and can be conveniently popularized to various materials with different compositions and shapes.
Drawings
In order to more clearly illustrate the technical solutions of the present invention or the prior art, the drawings needed for the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and those skilled in the art can also obtain other drawings according to the drawings without creative efforts.
FIG. 1 is a schematic structural diagram of a rechargeable organic calcium-ion battery according to an embodiment of the present invention;
FIG. 2 is an XRD pattern of MVOH, CVOH and SVOH in accordance with an embodiment of the present invention;
FIG. 3 is an SEM image of MVOH, CVOH and SVOH in accordance with an embodiment of the present invention;
FIG. 4 is a GITT graph of MVOH, CVOH and SVOH in accordance with an embodiment of the present invention;
FIG. 5 is a graph of the electrochemical performance characterization of MVOH, CVOH, and SVOH in accordance with an embodiment of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
It should be noted that in the description of the embodiments herein, the description of the term "some embodiments" means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. Throughout this specification, the schematic representations of the terms used above do not necessarily refer to the same implementation or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The term "in.. range" as used herein includes both ends, such as "in the range of 1 to 100" including both ends of 1 and 100.
The embodiment of the invention provides a rechargeable organic calcium ion battery, which comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the diaphragm and the electrolyte are arranged between the positive plate and the negative plate;
the positive plate comprises a positive current collector and a positive material, wherein the positive material comprises a positive active material, and the positive active material is a layered vanadium oxide which can allow cations forming calcium salt to be reversibly embedded and removed;
the negative plate comprises activated carbon cloth or metal calcium, and both the activated carbon cloth or the metal calcium can be used as a negative current collector and a negative active material;
the electrolyte comprises electrolyte calcium salt, organic solvent and/or ionic liquid.
Specifically, the molecular formula of the vanadium oxide is MxVyOz·nH2O, wherein M is a metal ion and comprises one of magnesium Mg, calcium Ca or strontium Sr; x is in the range of 0<x<0.5, y is in the range of 0<y<20, z is in the range of 0<z<20, n is in the range of 0<n<2。
Preferably, the vanadium oxide is M0.25V2O5·H2O，M0.26V2O5·H2O，M0.42V2O5·0.7H2O and M are metal ions and comprise one of magnesium Mg, calcium Ca or strontium Sr.
The membrane comprises one of a glass fiber membrane, a polytetrafluoroethylene membrane and filter paper.
The soluble salt of the electrolyte calcium is solute, the organic solvent is solvent, the concentration is in the range of 0.1mol/L to 1.0mol/L, the electrolyte calcium salt is liquid material with ion conductivity, and the electrolyte calcium salt comprises calcium hexafluorophosphate or calcium bistrifluoromethylsulfonyl imide.
The invention discovers that calcium ions can be reversible in the vanadium oxide material M in the organic electrolyte for the first timexVyOz·nH2And (3) performing de-intercalation in O, taking calcium ions with low cost and rich resources as an energy storage medium, and realizing the reversible charge-discharge process of the calcium ion secondary battery by embedding and de-intercalation of the calcium ions on the positive electrode active material. The rechargeable organic calcium ion battery provided by the invention has the characteristics of safety, environmental protection, low cost, high capacity and good cyclicity; in addition, the calcium salt is used for replacing the lithium salt, so that the application of the lithium salt is not limited by lithium resources, the development can be greatly improved, and the production cost of the battery is obviously reduced because the price of the calcium salt is far lower than that of the lithium salt.
Referring to fig. 1, the rechargeable organic calcium ion battery provided by the invention has the working principle that one side of the negative electrode is as follows: adsorption/desorption PF6 -Or TFSI-(ii) a Positive electrode side: ca of layered vanadium oxide2+Reversible intercalation/deintercalation. The organic calcium ion battery material provided by the invention has larger interlayer spacing and a stable 'pillar' structure, so that the organic calcium ion battery material has high capacity and good cyclicity.
Another embodiment of the present invention provides a method for preparing a rechargeable organic calcium-ion battery, which is used for preparing the rechargeable organic calcium-ion battery, and comprises the following steps:
s1, preparing a positive plate: mixing vanadium oxide, a conductive agent and a binder into slurry according to a certain proportion to prepare a positive electrode material, uniformly coating the positive electrode material on the surface of a positive electrode current collector, drying and cutting to obtain a positive electrode plate;
s2, preparing a negative plate: the metallic calcium or the activated carbon cloth is used as a negative plate after surface treatment;
s3, preparing electrolyte: adding electrolyte calcium salt into an organic solvent and/or ionic liquid, and stirring and mixing to obtain an electrolyte;
s4, preparing a diaphragm: cutting a glass fiber diaphragm, a polytetrafluoroethylene diaphragm or filter paper into required sizes, and drying to obtain a diaphragm;
and S5, tightly stacking the positive plate, the diaphragm and the negative plate in sequence, adding electrolyte to completely soak the diaphragm, and then packaging the stacked part into a battery shell to obtain the rechargeable organic calcium ion battery.
Specifically, in S1, the positive electrode current collector includes one of a copper foil, an aluminum foil, a titanium foil, a molybdenum foil, nickel foam, and a stainless steel foil, the conductive agent includes one of acetylene black, ketjen black, activated carbon, carbon fiber, and graphite carbon nanotube, and the binder includes one of polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC), and Polytetrafluoroethylene (PTFE).
The positive electrode material comprises 60-90% of vanadium oxide, 5-30% of conductive agent and 5-10% of binder by weight percentage.
Wherein the coating thickness of the positive electrode material on the surface of the positive electrode current collector in S1 is in the range of 60-200 μm. The surface treatment in S2 includes washing with ethanol, isopropanol or water, and then drying.
The preparation method has low requirement on equipment, simple and feasible process, short operation period and easy expanded production, the electrolyte adopts organic calcium ion electrolyte, and the cathode adopts carbon cloth or metal calcium material with rich resources and low price; the method has the characteristics of strong universality, simple process, programmable process and excellent electrochemical performance of the obtained material, and can be conveniently popularized to various materials with different compositions and shapes.
On the basis of the above embodiments, the present invention will be further illustrated by the following specific examples of the method of manufacturing a rechargeable organic calcium-ion battery. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are examples of experimental procedures not specified under specific conditions, generally according to the conditions recommended by the manufacturer. Unless otherwise indicated, percentages and parts are by mass.
Example 1
This example provides a method for preparing a rechargeable organic calcium ion battery, positive electrodeThe physical substance adopts Mg0.25V2O5·H2O, the negative pole is made of carbon cloth, the diaphragm is made of a glass fiber diaphragm, and the electrolyte is 0.3mol/L bis (trifluoromethyl) sulfonyl imide calcium, which comprises the following steps:
1)Mg0.25V2O5·H2preparation of O positive plate
Dissolving binder polyvinylidene fluoride (PVDF) or Polytetrafluoroethylene (PTFE) in N-methylpyrrolidone (NMP) to obtain clear solution, adding a certain amount of Mg0.25V2O5·H2And grinding the O nanobelt positive electrode material uniformly, adding the ground O nanobelt positive electrode material into the solution (according to the active substance, acetylene black and adhesive, the ratio of 7:2:1), stirring and dispersing to prepare slurry, uniformly coating the slurry on an aluminum foil with the thickness of 0.05mm, wherein the thickness of the coating layer is 120 microns, and drying in vacuum to obtain the positive electrode plate.
2) Preparing an electrolyte: dissolving a certain amount of bis (trifluoromethyl) sulfimide calcium salt in an organic solvent to prepare electrolyte with the concentration of 0.3 mol/L.
3) Preparing a negative plate: the activated carbon cloth is washed for several times by alcohol and acetone, and a wafer with the diameter of 12mm is obtained by punching and is used as a negative plate.
4) Assembly of organic calcium ion battery
And separating the positive plate and the negative plate by using a glass fiber membrane with the thickness of 0.2mm, putting the positive plate and the negative plate into a battery shell, respectively injecting electrolyte, and finally packaging the battery.
For Mg prepared in example 10.25V2O5·H2The O material was characterized for structural and electrical properties, resulting in the graphs shown in fig. 2-5. In addition, MVOH represents Mg0.25V2O5·H2O material or Mg0.25V2O5·H2O is calcium ion battery assembled by positive plate, CVOH represents Ca0.26V2O5·H2O material or Ca0.26V2O5·H2Calcium ion battery assembled by taking O as positive plate and SVOH as Sr0.42V2O5·0.7H2O material or Sr0.42V2O5·0.7H2And O is the calcium ion battery assembled by the positive plate.
Fig. 2 is an XRD pattern of MVOH, CVOH and SVOH, and as can be seen from fig. 2, X-ray diffraction analysis shows a layered material. FIG. 3 is an SEM image of MVOH, CVOH and SVOH, from which Mg can be seen0.25V2O5·H2The shape of the O material is a nanoribbon structure.
FIG. 4 is a GITT graph of MVOH, CVOH and SVOH as described in the examples, and it can be seen from FIG. 4 that the discharge capacity of MVOH was 317.2mA h g when the GITT charge and discharge test was performed at a low current density-1This corresponds to 1.22mol of calcium ions intercalated in the host material. The calcium ion battery positive electrode active material has excellent electrochemical performance.
FIG. 5 is the electrochemical performance of MVOH, CVOH and SVOH as described in the examples for three cathodes at 50 deg.C with 100mA g-1Lower cycling stability plot; as can be seen from FIG. 5, the MVOH capacity remained 198.4mA hr g after 100 cycles-1。
In conclusion, the rechargeable organic calcium ion battery prepared by the invention has the advantages of high specific capacity, long cycle life, simple process and low cost, and has wide application prospect in the aspect of large-scale energy storage.
Example 2
This example provides a method for preparing a rechargeable organic calcium ion battery, which is different from example 1 in that:
in step 1), Ca0.26V2O5·H2Preparing an O positive plate, comprising:
dissolving binder polyvinylidene fluoride (PVDF) or Polytetrafluoroethylene (PTFE) in N-methylpyrrolidone (NMP) to obtain clear solution, adding certain amount of Ca0.26V2O5·H2Grinding the O material uniformly, adding the ground O material into the solution (according to the active substance, acetylene black and adhesive, the ratio of 7:2:1), dispersing by ultrasonic to prepare slurry, uniformly coating the slurry on a titanium foil with the thickness of 0.05mm, wherein the thickness of the coating layer is 120 mu m, and drying in vacuum to obtain a positive plate;
the remaining steps and parameters were the same as in example 1.
Ca prepared in example 20.26V2O5·H2The O material was characterized for structural and electrical properties, resulting in the graphs shown in fig. 2-5.
As shown in FIG. 2, Ca0.26V2O5·H2The O material was shown to be a layered material by X-ray diffraction analysis, with a nanoribbon structure in morphology (as shown in fig. 3). Ca0.26V2O5·H2As shown in figure 4, the O shows excellent electrochemical performance when used as the anode active material of the calcium ion battery, and the discharge capacity is 311mA h g respectively when the GITT charge-discharge test is carried out at low current density-1This corresponds to 1.22mol of calcium ions intercalated in the host material.
FIG. 5 is a graph of the electrochemical performance of MVOH, CVOH and SVOH of an embodiment of the present invention with three cathodes at 50 deg.C of 100mA g-1Lower cycling stability plot; as can be seen from FIG. 5, the CVOH capacity remained 182.2mA hr g after 100 cycles-1。
Example 3
This example provides a method for preparing a rechargeable organic calcium ion battery, which is different from example 1 in that:
in step 1), Sr0.42V2O5·0.7H2Preparing an O positive plate, comprising:
dissolving polyvinylidene fluoride (PVDF) or Polytetrafluoroethylene (PTFE) as binder in N-methylpyrrolidone (NMP) to obtain clear solution, adding a certain amount of Sr0.42V2O5·0.7H2Grinding the O material uniformly, adding the ground O material into the solution (according to the active substance, acetylene black and adhesive, the ratio of 7:2:1), dispersing by ultrasonic to prepare slurry, uniformly coating the slurry on a titanium foil with the thickness of 0.05mm, wherein the thickness of the coating layer is 120 mu m, and drying in vacuum to obtain a positive plate;
the remaining steps and parameters were the same as in example 1.
Sr prepared in example 30.42V2O5·0.7H2The O material is subjected to structural and electrical property characterization to obtain the structure shown in FIG. 2-Figure 5 shows the results.
As shown in FIG. 2, Sr0.42V2O5·0.7H2The O material was shown to be a layered material by X-ray diffraction analysis, with a nanoribbon structure in morphology (as shown in fig. 3). Sr0.42V2O5·0.7H2As shown in figure 4, the O shows excellent electrochemical performance when used as the positive electrode active material of the calcium ion battery, and the discharge capacity is 269.9mA h g respectively when the GITT charge-discharge test is carried out at low current density-1This corresponds to 1.16mol of calcium ions intercalated into the host material. FIG. 5 shows the electrochemical performance of MVOH, CVOH and SVOH of the present invention with three anodes at 50 deg.C with 100mA g-1Lower cycling stability plot; as can be seen in FIG. 5, after 100 cycles, the SVOH capacity remained at 193.3mA hr g-1。
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.
Claims (10)
1. A rechargeable organic calcium ion battery is characterized by comprising a positive plate, a negative plate, a diaphragm and electrolyte, wherein the diaphragm and the electrolyte are arranged between the positive plate and the negative plate;
the positive plate comprises a positive current collector and a positive material, wherein the positive material comprises a positive active material, and the positive active material is a layered vanadium oxide capable of allowing cations forming calcium salt to be reversibly embedded and removed;
the negative plate comprises activated carbon cloth or metal calcium, and both the activated carbon cloth or the metal calcium can be used as a negative current collector and a negative active material;
the electrolyte comprises an electrolyte calcium salt, an organic solvent and/or an ionic liquid.
2. The rechargeable organocalcium-ion battery according to claim 1, characterized in that the vanadium oxide has the formula MxVyOz·nH2O, wherein M is a metal ion and comprises one of magnesium, calcium or strontium; x is in the range of 0<x<0.5, y is in the range of 0<y<20, z is in the range of 0<z<20, n is in the range of 0<n<2。
3. The rechargeable organic calcium-ion battery of claim 1, wherein the membrane comprises one of a glass fiber membrane, a polytetrafluoroethylene membrane, and filter paper.
4. The rechargeable organic calcium-ion battery according to any one of claims 1 to 3, wherein the electrolyte calcium salt comprises calcium hexafluorophosphate or calcium bistrifluoromethylsulfonimide.
5. The rechargeable organic calcium-ion battery according to claim 4, wherein the concentration of the electrolyte is in the range of 0.1 to 1.0 mol/L.
6. A method for preparing a rechargeable organic calcium-ion battery, for preparing a rechargeable organic calcium-ion battery according to any one of claims 1 to 5, comprising the steps of:
s1, preparing a positive plate: mixing vanadium oxide, a conductive agent and a binder into slurry according to a certain proportion to prepare a positive electrode material, uniformly coating the positive electrode material on the surface of a positive electrode current collector, drying and cutting to obtain the positive electrode plate;
s2, preparing a negative plate: performing surface treatment on metallic calcium or activated carbon cloth to obtain the negative plate;
s3, preparing electrolyte: adding electrolyte calcium salt into an organic solvent and/or ionic liquid, and stirring and mixing to obtain the electrolyte;
s4, preparing a diaphragm: cutting a glass fiber diaphragm, a polytetrafluoroethylene diaphragm or filter paper into required sizes, and drying to obtain the diaphragm;
and S5, tightly stacking the positive plate, the diaphragm and the negative plate in sequence, adding the electrolyte to completely infiltrate the diaphragm, and then packaging the stacked part into a battery shell to obtain the rechargeable organic calcium ion battery.
7. The method according to claim 6, wherein the positive electrode current collector in step S1 includes one of a copper foil, an aluminum foil, a titanium foil, a molybdenum foil, a nickel foam, and a stainless steel foil, the conductive agent includes one of acetylene black, ketjen black, activated carbon, carbon fiber, and graphite carbon nanotube, and the binder includes one of polyvinylidene fluoride, sodium carboxymethylcellulose, and polytetrafluoroethylene.
8. The production method according to claim 7, characterized in that the positive electrode material comprises, in weight percent, 60-90% of the vanadium oxide, 5-30% of the conductive agent, and 5-10% of the binder.
9. The production method according to claim 7 or 8, characterized in that the coating thickness of the positive electrode material on the surface of the positive electrode current collector in step S1 is in a range of 60 μm to 200 μm.
10. The method of claim 6, wherein the surface treatment in step S2 includes washing with ethanol, isopropanol, or water, and then drying.
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| CN114566647A (en) * | 2022-02-09 | 2022-05-31 | 武汉理工大学 | Calcium phosphate coated high-nickel ternary cathode material and preparation method and application thereof |
| CN114566647B (en) * | 2022-02-09 | 2023-05-12 | 武汉理工大学 | Calcium phosphate coated high-nickel ternary positive electrode material and preparation method and application thereof |
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