CN112838206B - Layered oxide cathode material with excellent air stability and method for improving air stability by adjusting sodium content - Google Patents
Layered oxide cathode material with excellent air stability and method for improving air stability by adjusting sodium content Download PDFInfo
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Abstract
The invention discloses a layered oxide cathode material with excellent air stability and a method for improving the air stability by adjusting the sodium content. The layered oxide anode material is O3 phase and has a chemical formula of NaxMeO2Wherein Me at least contains one or more elements of Li, Ni, Fe, Co and Mn, and x is the stoichiometric number of Na and is 0.93 ⩽ x ⩽ 0.95.95. According to the invention, the content of sodium ions in the layered positive electrode material of the sodium ion battery O3 is reduced, the strength of Na-O bonds is enhanced, the probability of reaction with the outside is reduced, meanwhile, the valence state of transition metal ions in the material is improved, the oxidation resistance of the transition metal ions is improved, and further, the electrode material with more excellent air stability is obtained. The synthesis method is simple and easy to operate, the raw materials are rich and low in price, and the practical application degree is high, so that the invention provides new insight for the optimized design of the high-performance sodium-ion battery layered positive electrode material, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of electrochemical power sources, and particularly relates to a layered oxide cathode material with excellent air stability and a method for improving the air stability by adjusting the sodium content.
Background
At present, energy and environment serve as two problems facing the current society to guide the life and development of people in all aspects, and the development and the utilization of clean energy are very urgent. However, the utilization of uncontrollable energy forms such as wind energy and solar energy puts high demands on the development of energy storage systems with high efficiency, safety and low price. On one hand, the sodium ion battery has performance advantages comparable to that of the lithium ion battery, and on the other hand, the sodium ion battery shows strong competitiveness in the field of large-scale energy storage devices due to the abundant sodium resources. Research on the positive electrode material of sodium ions is crucial to the development of sodium ion batteries. Among many sodium-based positive electrode materials, a layered metal oxide of the O3 type has been paid attention and studied by various parties because of its high electrochemical activity and simple preparation process.
However, due to the poor air stability of the layered oxide cathode material, the material is urgently required to be protected in an inert gas filled environment after being prepared. This has resulted in significant limitations in the transportation and use of such materials in practical production processes. Therefore, improving the air stability of such materials by finding a viable approach is a key driving the further development of alkali metal ion batteries.
Disclosure of Invention
The invention aims to provide a layered oxide cathode material with excellent air stability and a method for improving the air stability by adjusting the sodium content.
In order to achieve the purpose, the invention adopts the following technical scheme:
the present invention firstly provides a sodium-based layered oxide positive electrode material which is stable in air. The layered oxide anode material is specifically O3 phase with the chemical formula of NaxMeO2Wherein Me at least contains one or more elements of Li, Ni, Fe, Co and Mn, x is the stoichiometric number of sodium, and is usually more than or equal to 0.93 and less than or equal to 0.95, and each element in the chemical formula satisfies the charge balance.
The invention further provides a method for improving the air stability of the material by reducing the content of sodium ions in the synthetic material. Under the same condition of Me, the electrostatic attraction capacity of Na ions and O ions is enhanced by reducing the content of Na between layers, the state of the Na ions in the structure is stabilized, and the escape of the Na ions between the layers is inhibited; meanwhile, due to the reduction of the Na content, according to the principle of electronegativity conservation, the valence state of the transition metal is improved, the oxidation resistance of the material is improved, and further the electrode material with more excellent air stability is obtained.
The invention also provides a preparation method of the layered oxide cathode material, which comprises the following steps: and uniformly mixing the metal salt and the metal oxide in the corresponding proportion at the early stage, tabletting, and then heating and calcining in a program manner to obtain the cathode material.
In the preparation method, the calcination temperature is 700-1000 ℃, preferably 950 ℃; the calcination time is 12-24h, preferably 24 h; in the heating step, the heating rate is 2-10 ℃ min-1Preferably 3 ℃ min-1。
The invention also provides a composite electrode for a sodium ion battery, which contains NaxTmO2Materials, binders, conductive additives and solvents.
In the composite electrode, the conductive additive is one or more of carbon black, Super-P and Ketjen black, and the Super-P is preferred.
In the composite electrode, the binder is one or more of polyvinylidene fluoride (PVDF) or polyacrylic acid (PAA), sodium carboxymethylcellulose (CMC), Sodium Alginate (SA) and gelatin, and is preferably PVDF.
In the composite electrode, the solvent is N-methylpyrrolidone.
The invention also provides a preparation method of the composite electrode, which comprises the following steps: mixing NaxTmO2The material is mixed with conductive additive, adhesive and solvent according to a certain proportion, and the composite electrode is prepared by the technological processes of pulping, smearing, drying and the like.
The invention also provides an energy storage element, wherein the energy storage element contains NaxTmO2The energy storage element is preferably a sodium ion battery. Na (Na)xTmO2The material can be used as a positive electrode material of a sodium ion secondary battery.
The sodium ion battery provided by the invention comprises the composite electrode as a positive electrode, a diaphragm, an organic electrolyte and metal sodium as a negative electrode.
In the sodium ion battery, the organic electrolyte is a carbonate electrolyte, and the concentration of the carbonate electrolyte is 0.1-2M, preferably 1M.
In the carbonate electrolyte, the solvent is at least one selected from dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), Ethylene Carbonate (EC) and Propylene Carbonate (PC), preferably PC; the solute is selected from sodium hexafluorophosphate (NaPF)6) Sodium perchlorate (NaClO)4) Sodium bistrifluoromethylsulfonyl imide (NaTFSI), preferably sodium perchlorate (NaClO)4)。
The working temperature of the sodium ion battery is 25 ℃.
The method for improving the air stability of the sodium ion layered cathode material by reducing the sodium ion content has the advantages that the preparation process is simple and easy to implement, the raw material source is rich and wide, the content of sodium element in the product can be directly controlled by regulating and controlling the feeding ratio of the sodium source, and the prepared material has excellent air stability. The layered transition metal oxide shows excellent electrochemical stability when being used as a positive electrode material of a sodium ion battery, and the material can be directly used as an electrode material of the sodium ion battery. By reducing the content of sodium ions in the synthesized material in a proper amount, the combination of Na ions and O ions is stabilized, and H in the material and air is inhibited2O and CO2Molecules react, and the Na content is reduced, so that the probability of reaction with the outside is reduced; meanwhile, the valence state of the transition metal is improved, and the oxidation resistance of the material is improved, so that the air stability of the material is integrally improved, and the electrochemical performance of the layered anode material is optimized.
Compared with the prior art, the method successfully improves Na by regulating and controlling the content of the sodium source in the preparation processxMeO2Air stability of the positive electrode material of the sodium ion battery.
Drawings
FIG. 1 shows Na0.93Li0.12Ni0.25Fe0.15Mn0.48O2X-ray diffraction patterns of the sample before and after exposure to air;
FIG. 2 is NaLi0.12Ni0.25Fe0.15Mn0.48O2X-ray diffraction patterns of samples before and after exposure to air.
Detailed Description
The present invention will be further described with reference to the following specific examples.
The reagents and apparatus described in the following examples are commercially available unless otherwise specified.
Example 1
(one) preparation of Na0.93Li0.12Ni0.25Fe0.15Mn0.48O2Positive electrode material
Weighing Na according to corresponding proportion2CO3、Li2CO3、NiO、Fe2O3、Mn2O3Ball-milling for 24h, pressing into a wafer with the diameter of 10mm under the pressure of 10MPa, and calcining for 24h at 950 ℃ by using a muffle furnace to obtain sample powder.
(II) para Na0.93Li0.12Ni0.25Fe0.15Mn0.48O2XRD testing of the sample powders
Obtaining Na by using X-ray diffractometer by utilizing diffraction effect of X-rays in crystalline substance0.93Li0.12Ni0.25Fe0.15Mn0.48O2The XRD pattern of the sample powder was used to perform an efficient analysis of the material with reference to a standard PDF card.
(III) preparation of Na0.93Li0.12Ni0.25Fe0.15Mn0.48O2Composite positive electrode
And uniformly mixing the prepared anode material with a conductive additive Super-P and a binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8: 1, adding a proper amount of N-methylpyrrolidone, and performing processes such as pulping, smearing, drying and the like to obtain the composite anode.
(IV) assembling sodium ion battery
Assembling the prepared composite anode and a sodium cathode into a sodium ion battery, wherein the electrolyte is selected from a carbonate electrolyte (1M NaClO)4PC (5% FEC) solution).
(V) sodium ion Battery test
The above sodium ion battery was subjected to charge and discharge tests at a constant rate of 0.2C (1C ═ 200mAh/g) using a blue charge and discharge system.
(VI) Exposure test
Mixing Na0.93Li0.12Ni0.25Fe0.15Mn0.48O2And (3) exposing the sample powder in an environment with stable humidity and temperature, performing XRD (X-ray diffraction) test on the sample powder after one day to analyze the material structure, and repeating the two, three, four and five steps after two days to perform electrochemical test on the sample.
Example 2
(one) preparation of Na0.93Li0.12Ni0.25Fe0.2Mn0.43O2Positive electrode material
Weighing Na according to corresponding proportion2CO3、Li2CO3、NiO、Fe2O3、Mn2O3Ball-milling for 24h, pressing into a wafer with the diameter of 10mm under the pressure of 10MPa, and calcining for 24h at 950 ℃ by using a muffle furnace to obtain sample powder.
(II) para Na0.93Li0.12Ni0.25Fe0.2Mn0.43O2XRD testing of the sample powder and analysis of the data were carried out (the same procedure as in example 1)
(III) preparation of Na0.93Li0.12Ni0.25Fe0.2Mn0.43O2Composite positive electrode (the concrete steps are the same as those in example 1)
(IV) assembling sodium ion battery (the concrete steps are the same as those of example 1)
(V) sodium ion Battery test (the same procedure as in example 1)
(VI) Exposure test (the same procedure as in example 1)
Example 3
(one) preparation of Na0.93Li0.12Ni0.25Co0.15Mn0.48O2Positive electrode material
Weighing Na according to corresponding proportion2CO3、Li2CO3、NiO、Co3O4、Mn2O3Ball-milling for 24h, pressing into a wafer with the diameter of 10mm under the pressure of 10MPa, and calcining for 24h at 950 ℃ by using a muffle furnace to obtain sample powder.
(II) para Na0.93Li0.12Ni0.25Co0.15Mn0.48O2XRD testing of the sample powder and analysis of the data were carried out (the same procedure as in example 1)
(III) preparation of Na0.93Li0.12Ni0.25Co0.15Mn0.48O2Composite positive electrode (the concrete steps are the same as those in example 1)
(IV) assembling sodium ion battery (the concrete steps are the same as those of example 1)
(V) sodium ion Battery test (the same procedure as in example 1)
(VI) Exposure test (the same procedure as in example 1)
Example 4
(I) preparation of Na0.93Li0.12Ni0.25Co0.2Mn0.43O2And (3) a positive electrode material.
Weighing Na according to corresponding proportion2CO3、Li2CO3、NiO、Co3O4、Mn2O3Ball-milling for 24h, pressing into a wafer with the diameter of 10mm under the pressure of 10MPa, and calcining for 24h at 950 ℃ by using a muffle furnace to obtain sample powder.
(II) para Na0.93Li0.12Ni0.25Co0.2Mn0.43O2XRD testing of the sample powder and analysis of the data were carried out (the same procedure as in example 1)
(III) preparation of Na0.93Li0.12Ni0.25Co0.2Mn0.43O2Composite positive electrode (the concrete steps are the same as those in example 1)
(IV) assembling sodium ion battery (the concrete steps are the same as those of example 1)
(V) sodium ion Battery test (the same procedure as in example 1)
(VI) Exposure test (the same procedure as in example 1)
Comparative example 1
(one) preparation of NaLi0.12Ni0.25Fe0.15Mn0.48O2Positive electrode material
Weighing Na according to corresponding proportion2CO3、Li2CO3、NiO、Fe2O3、Mn2O3Ball-milling for 24h, pressing into a wafer with the diameter of 10mm under the pressure of 10MPa, and calcining for 24h at 950 ℃ by using a muffle furnace to obtain sample powder.
(II) para-NaLi0.12Ni0.25Fe0.15Mn0.48O2XRD testing of the sample powder and analysis of the data were carried out (the same procedure as in example 1)
(III) preparation of NaLi0.12Ni0.25Fe0.15Mn0.48O2Composite positive electrode (the concrete steps are the same as those in example 1)
(IV) assembling sodium ion battery (the concrete steps are the same as those of example 1)
(V) sodium ion Battery test (the same procedure as in example 1)
(VI) Exposure test (the same procedure as in example 1)
Comparative example 2
(one) preparation of NaLi0.12Ni0.25Fe0.2Mn0.43O2Positive electrode material
Weighing Na according to corresponding proportion2CO3、Li2CO3、NiO、Fe2O3、Mn2O3Ball-milling for 24h, pressing into a wafer with the diameter of 10mm under the pressure of 10MPa, and calcining for 24h at 950 ℃ by using a muffle furnace to obtain sample powder.
(II) para-NaLi0.12Ni0.25Fe0.2Mn0.43O2XRD testing of the sample powder and analysis of the data (procedures same as example 1)
(III) preparation of NaLi0.12Ni0.25Fe0.2Mn0.43O2Composite positive electrode (the concrete steps are the same as those in example 1)
(IV) assembling sodium ion battery (the concrete steps are the same as those of example 1)
(V) sodium ion Battery test (the same procedure as in example 1)
(VI) Exposure test (the same procedure as in example 1)
Comparative example 3
(one) preparation of NaLi0.12Ni0.25Co0.15Mn0.48O2Positive electrode material
Weighing Na according to corresponding proportion2CO3、Li2CO3、NiO、Co3O4、Mn2O3Ball-milling for 24h, pressing into a wafer with the diameter of 10mm under the pressure of 10MPa, and calcining for 24h at 950 ℃ by using a muffle furnace to obtain sample powder.
(II) para-NaLi0.12Ni0.25Co0.15Mn0.48O2XRD testing of the sample powder and analysis of the data were carried out (the same procedure as in example 1)
(III) preparation of NaLi0.12Ni0.25Co0.15Mn0.48O2Composite positive electrode (the concrete procedure is the same as in example 1)
(IV) assembling sodium ion battery (the concrete steps are the same as those of example 1)
(V) sodium ion Battery test (the same procedure as in example 1)
(VI) Exposure test (the same procedure as in example 1)
Comparative example 4
(one) preparation of NaLi0.12Ni0.25Co0.2Mn0.43O2Positive electrode material
Weighing Na according to corresponding proportion2CO3、Li2CO3、NiO、Co3O4、Mn2O3Ball-milling for 24h, pressing into a wafer with the diameter of 10mm under the pressure of 10MPa, and calcining for 24h at 950 ℃ by using a muffle furnace to obtain sample powder.
(II) to NaLi0.12Ni0.25Co0.2Mn0.43O2XRD testing of the sample powder and analysis of the data (procedures same as example 1)
(III) preparation of NaLi0.12Ni0.25Co0.2Mn0.43O2Composite positive electrode (the concrete steps are the same as those in example 1)
(IV) assembling sodium ion battery (the concrete steps are the same as those of example 1)
(V) sodium ion Battery test (the same procedure as in example 1)
(VI) Exposure test (the same procedure as in example 1)
TABLE 1
The above examples show that the high temperature solid phase method reduces the content of sodium in the anode layered oxide material, reduces the degree of the interlayer Na ions affected by the external environment, and inhibits the Na ions from reacting with H2O and CO2The molecules react, thereby improving the air stability of the material. From the comparison of the X-ray diffraction patterns of examples 1, 2, 3 and 4 and comparative examples 1, 2, 3 and 4, it is found that by reducing the content of sodium ions in the layered positive electrode material of the sodium-ion battery, a significant O '3 monoclinic phase appears after comparative example 1 is exposed in the air, while the material prepared in example 1 after the content of sodium is reduced still maintains the O3 phase of the material, the generation of the O'3 monoclinic phase is inhibited, the air stability of the material is remarkably improved, and this is related to the fact that after the content of Na is reduced, the valence state of the transition metal is improved, and thus the oxidation resistance of the material is improved. In addition, the influence of the outside air can reduce the number of active Na ions between material layers and reduce the capacity of the electrode, which can be reflected in the electrochemical performance of each proportion, and the electrochemical performance of each improved embodiment keeps good without obvious reduction.
In conclusion, the layered oxide cathode material applied to the sodium-ion battery has excellent air stability, and effectively inhibits the generation of a new phase of the material after air exposure by reducing the content of Na between layers, thereby maintaining the electrochemical performance of the material. The corresponding composite electrode has the advantages of simple preparation method, easily obtained raw materials and low price, so the invention can provide new insight for the performance optimization design of the high-capacity sodium ion battery anode laminated material structure, and has wide application prospect.
The above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the embodiments of the present invention, and those skilled in the art can easily make various changes or modifications according to the main concept and spirit of the present invention, so the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A layered oxide cathode material with excellent air stability is characterized in that: the layered oxide anode material is O3 phase with chemical formula of NaxMeO2Wherein Me at least contains one or more elements of Li, Ni, Fe, Co and Mn, and x is the stoichiometric number of Na and is 0.93 ⩽ x<0.95。
2. The method for producing a layered oxide positive electrode material excellent in air stability according to claim 1, characterized in that: the anode material is prepared by grinding and uniformly mixing metal oxides in corresponding proportion, tabletting, and then heating and calcining in a program manner.
3. The method for producing a layered oxide positive electrode material excellent in air stability according to claim 2, characterized in that: the calcination temperature is 700-1000 ℃, the calcination time is 12-24h, and the heating rate is 2-10 ℃ for min in the heating process-1。
4. The method for producing a layered oxide positive electrode material excellent in air stability according to claim 3, characterized in that: the calcination temperature is 950 ℃, the calcination time is 24h, and the heating rate is 3 ℃ for min in the heating process-1。
5. A composite electrode comprising the layered oxide positive electrode material according to claim 1, characterized in that: the composite electrode contains the positive electrode material, a conductive additive, a binder and a solvent; the conductive additive is one or more of carbon black, Super-P and Ketjen black; the binder is one or more of polyvinylidene fluoride, polyacrylic acid, sodium carboxymethylcellulose, styrene butadiene rubber/sodium carboxymethylcellulose, sodium alginate and gelatin; the solvent is N-methyl pyrrolidone.
6. The method of synthesizing a composite electrode according to claim 5, wherein: the anode material is prepared by pulping, smearing and drying processes, wherein the content of the anode material is 80 wt%, the content of the conductive additive is 10 wt%, and the content of the binder is 10 wt%.
7. A sodium ion battery, characterized by: the anode consists of an anode, a diaphragm, organic electrolyte and cathode metal sodium; the positive electrode is the composite electrode of claim 5; the organic electrolyte is a carbonate electrolyte with the concentration of 0.1-2M; in the carbonate electrolyte, a solvent is selected from at least one of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate and propylene carbonate; the solute is at least one selected from sodium hexafluorophosphate, sodium perchlorate and sodium bistrifluoromethylsulfonyl imide.
8. A method for improving the air stability of a layered oxide cathode material by adjusting the sodium content is characterized in that: the chemical formula of the layered oxide cathode material is NaxMeO2Wherein Me at least contains one or more elements of Li, Ni, Fe, Co and Mn, x is the stoichiometric number of Na, and the content of Na in the interlayer is reduced to 0.93 ⩽ x under the same condition of Me<0.95, the electrostatic attraction capacity of Na ions and O ions is enhanced, the state of the Na ions in the structure is stabilized, and the escape of Na ions between layers is inhibited; meanwhile, due to the reduction of the Na content, the valence state of the transition metal is improved and the material is improved according to the principle of electronegativity conservationOxidation resistance, and further an electrode material with more excellent air stability is obtained.
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| CN115626669B (en) * | 2022-12-20 | 2023-04-25 | 江苏正力新能电池技术有限公司 | Conversion type material synergistic modified sodium ion battery O3 phase layered oxide cathode material and preparation method and application thereof |
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