CN115939368A - Layered oxide cathode material with low volume change in charging and discharging processes and preparation method thereof - Google Patents
Layered oxide cathode material with low volume change in charging and discharging processes and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 18
- 238000007599 discharging Methods 0.000 title abstract description 9
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
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- 239000010405 anode material Substances 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 4
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 4
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- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
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- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
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- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
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Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a layered oxide cathode material with low volume change in the charge and discharge process and a preparation method thereof, wherein the general formula of the layered oxide cathode material is Na x M a [M b Ni c Mn d ]O 2 Wherein Ni and Mn are transition metal elements, ma and Mb are metal elements substituted by Na layer and transition metal layer, and Ma is Mg 2+ 、Ca 2+ And Zn 2+ Mb is Li + 、Al 3+ 、K+、Ti 4+ 、V 3+ 、Cr 5+ 、Fe 3+ 、Co 3+ And Cu 2+ X is more than or equal to 0.67 and less than or equal to 0.85, a is more than or equal to 0.03 and less than or equal to 0.1, b is more than or equal to 0.05 and less than or equal to 0.3, b + c + d is more than or equal to 0.9 and less than or equal to 1, c is more than or equal to 0.03 and less than or equal to 0.3, and d is more than or equal to 0.6 and less than or equal to 0.7. In thatIn the Na layer, the electrochemical inactive metal is taken as a support column of the material, so that the material is supported, and the material cannot slide in the charging and discharging process; in transition metal layers, ni mitigation by element substitution 2+/4+ And Mn 3+/4+ The Jhan-Teller effect is initiated. The positive electrode material has no P2-O2 phase change in the charging and discharging processes, so that the volume change rate of the material is reduced, and the cycle life of the material is prolonged.
Description
Technical Field
The invention belongs to the technical field of sodium battery materials, and relates to a layered oxide cathode material with low volume change in the charging and discharging processes and a preparation method thereof.
Background
Sodium Ion Batteries (SIBs) are promising candidates for large-scale energy storage systems due to their advantages such as low cost and similar physicochemical properties as lithium ion batteries. For sodium ion batteries, the energy density and operating voltage of the positive electrode material are greatly limited. The research on the high-performance low-cost cathode material is very critical for the development of the sodium ion battery. Currently, positive electrode materials generally considered to have application prospects include transition metal layered oxides, polyanion compounds, prussian blue compounds, and organic compounds. Wherein the transition metal layered oxide NaxTMO 2 (TM: transition metal, ti, mn, fe, co, ni, cu. Etc.) has a large practical application potential due to simple synthesis, excellent electrochemical performance and convenience of industrialization.
The P2 type layered oxide has high reversible specific capacity and a stable crystal structure, so that the P2 type layered oxide is a sodium ion battery anode material with great potential. Representative P2-Na 2/3 Ni 1/3 Mn 2/3 O 2 Has higher capacity and working voltage and is receiving wide attention. However, when the system is charged to about 4.2V, the content of sodium ions in the system is low, the electrostatic repulsive force between two adjacent transition metal layers is increased, and the transition metal layers are driven to generate relative slip to reduce the capacity of the system to achieve a stable structure, and in the process, the so-called P2-O2 phase transition is generated. This would bring about a drastic volume change, resulting in structural failure and poor stability of the material.
How to solve the problem that the Ni-Mn-based material is in harmful P2-O2 phase change in the charge and discharge process, reduce the volume change of the material, and improve the structural stability and the cycle life of the material is a problem to be solved urgently in the field.
Disclosure of Invention
In view of the above, the invention provides a layered oxide cathode material with low volume change in the charging and discharging processes and a preparation method thereof, which solve the problem of structural damage of the layered oxide caused by more Na ion deintercalation at high voltage, greatly improve the cycle life of the material, and have great practical value.
In a first aspect, the invention discloses a layered oxide cathode material with low volume change in the charge-discharge process, the chemical general formula is Na x M a [M b Ni c Mn d ]O 2 ；
Wherein Ni and Mn are transition metal elements, M a And M b Respectively, a metal element substituted by Na layer and transition metal layer, M a Is Mg 2+ 、Ca 2+ And Zn 2+ One or more elements of (2), M b Is Li + 、Al 3+ 、K + 、Ti 4+ 、V 3+ 、Cr 5+ 、Fe 3+ 、Co 3+ And Cu 2+ X, a, b, c and d are respectively the molar ratio of the corresponding elements, x is more than or equal to 0.67 and less than or equal to 0.85, a is more than or equal to 0.03 and less than or equal to 0.1, b is more than or equal to 0.05 and less than or equal to 0.3, b + c + d is more than or equal to 0.9 and less than or equal to 1, c is more than or equal to 0.03 and less than or equal to 0.3, and d is more than or equal to 0.6 and less than or equal to 0.7; each component satisfies charge conservation and stoichiometric conservation.
The molar ratio Mb/Ma is 1.5-3.
In another aspect, the present invention provides a method for preparing the layered oxide positive electrode material, including: will M b Mixing the oxide, carbonate, hydroxide or nitrate with a sodium source, and calcining to obtain a primary product; reacting the primary product with M a Mixing the oxide, carbonate, hydroxide, nitrate or acetate, and calcining for the second time to obtain a layered oxide cathode material; or mixing M a Of an oxide, carbonate, hydroxide or nitrate of, M b The oxide, carbonate, hydroxide, nitrate or acetate is mixed with a sodium source and calcined to obtain the layered oxide cathode material.
The sodium source is sodium carbonate, sodium nitrate or sodium acetate.
The calcining temperature is 850-1000 ℃, the calcining time is 8-24 h, and the calcining atmosphere is air, oxygen or nitrogen.
In a third aspect, the invention provides a positive electrode plate of a sodium ion secondary battery, which comprises the layered oxide positive electrode material. More specifically, the positive pole piece comprises a current collector, a conductive additive coated on the current collector, a binder and the layered oxide positive pole material.
In a fourth aspect, the invention also provides a sodium ion secondary battery, which comprises the positive pole piece.
The invention has the following beneficial effects:
elements such as Ni and Mn contained in the P2-type layered oxide anode material provided by the invention are nontoxic and safe elements; through element substitution, in the Na layer, the electrochemically inactive metal is used as a support column of the material to play a supporting role for the material, and the material cannot slide in the charging and discharging processes; in transition metal layers, ni mitigation by element substitution 2+/4+ And Mn 3+/4+ Based on the Jhan-Teller effect, the layered oxide positive electrode material used for the sodium ion secondary battery does not generate P2-O2 phase change in the charging and discharging processes, the volume change rate of the material is reduced, and the volume change is only 0.65%, so that the material has excellent cycle performance at 0.1mAg -1 The retention rate of the capacity after 150 times of circulation under the current density is 90.5 percent, and the capacity also has unusual specific capacity (130 mAh g) -1 ). Different from most P2 type oxide cathode materials sensitive to water, the material also shows excellent structural stability after being treated by water and air, the structure of the material is not changed after being aged in air and water, and the electrochemical performance is hardly attenuated. In addition, the layered oxide cathode material is prepared through simple high-temperature solid-phase reaction, is simple to operate, has low cost and is easy for industrial production. Therefore, the sodium ion full cell constructed by the layered oxide anode material has high energy density, long cycle life and great application value, and can be used for large-scale energy storage equipment such as solar energy, tidal energy and wind energy power generation, smart power grids, distributed power stations and the like。
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a graph of XRD test results for various embodiments of the present invention;
FIG. 2 is the charge-discharge curve of the first three cycles of example 1 under 0.1C magnification;
FIG. 3 is a graph of 150 cycles at 1C rate for examples 1 and 2, comparative examples 1 and 2, and comparative examples 3 of the present invention;
FIG. 4 is a diagram of the in-situ XRD test result of example 1 of the present invention under 0.2C magnification during the first cycle charge and discharge process;
FIG. 5 is a graph showing the results of XRD testing of example 1 of the present invention after aging in air and water;
FIG. 6 is a graph of the long cycle performance of example 1 of the present invention after aging in air and water;
FIG. 7 is the charge-discharge curve of the first three cycles at 0.1C magnification for example 2 of the present invention;
FIG. 8 is a charge-discharge curve of comparative example 1 of the present invention for the first three cycles at 0.1C magnification;
FIG. 9 is a charge-discharge curve of comparative example 2 of the present invention for the first three cycles at 0.1C magnification;
FIG. 10 is a charge-discharge curve of comparative example 3 of the present invention for the first three cycles at 0.1C magnification;
FIG. 11 is a first cycle charge-discharge curve at 0.1C rate of comparative example 4 of the present invention;
FIG. 12 is a first cycle charge and discharge curve at 0.1C rate of comparative example 5 of the present invention;
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the scope of the present invention is not limited thereto.
Example 1
Anhydrous sodium carbonate, lithium hydroxide monohydrate, nickel oxide and manganese dioxide are mixed according to the molar ratio of Na, li, ni and Mn of 0.75:0.15:0.1:0.7 mixing, grinding in an agate mortarFor further mixing, putting the materials in a planetary ball mill for continuous ball milling and mixing for 5h at the rotating speed of 400r/min to obtain a precursor; the obtained precursor tablets are mixed and transferred into a corundum boat, and are treated for 15 hours at 900 ℃ in a muffle furnace to obtain a black powder layered oxide material (primary product) Na 0.75 [Li 0.15 Ni 0.1 Mn 0.7 ]O 2 Mixing the layered oxide material powder with magnesium oxide in a molar ratio of Na to Mg of 0.75:0.05 mixing again, tabletting the mixture, and treating at 900 ℃ in a muffle furnace for 15h to obtain a black powder layered oxide cathode material Na 0.75 Mg 0.05 [Li 0.15 Ni 0.1 Mn 0.7 ]O 2 The XRD diffraction patterns are respectively shown in figure 1, and the material is a P2 phase layered oxide and a superlattice peak near 22.5 degrees is shown in the XRD results, so that the TM1/TM2 ordered arrangement exists in the material. It is known that the Mg sites of the TM layer can inhibit the ordered arrangement of the transition metal layer, which means that Mg in the material does not enter the TM layer but enters the Na layer.
The layered oxide obtained by the above preparation was used for the preparation of a sodium ion battery as a positive electrode active material, and specifically, the prepared layered oxide positive electrode material was mixed with Super-P and polyvinylidene fluoride (PVdF) in N-methyl-2-pyrrolidone (NMP) at a mass ratio of 8.5. And then uniformly coating the uniformly mixed slurry on an aluminum foil, and performing vacuum drying for 10 hours at the temperature of 100 ℃ to obtain the positive pole piece. The loading capacity of the positive pole piece is 3-4mg/cm 2 . CR2032 coin cells were assembled in an argon glove box with water and oxygen content less than 0.1 ppm. The layered oxide material was used as a positive electrode, a sodium sheet was used as a negative electrode, a glass fiber membrane GF/F was used as a separator in the middle, and the electrolyte was NaPF 6/(PC: FEC = 95). And in a 30 ℃ constant temperature box, performing constant current charge and discharge test on a blue battery test system, wherein the voltage interval is 2-4.35V. The test results are shown in fig. 2 and fig. 3, the reversible specific capacity can reach 130mAh/g, the material has good cycle performance, and the cycle capacity retention rate of the material is 90.5% after 150 times under the current density of 0.1 mAg-1.
And carrying out in-situ XRD (X-ray diffraction) test on the prepared layered oxide serving as the positive active material to calculate the volume change rate of the charge-discharge process of the layered oxide, wherein the specific steps comprise mixing slurry according to the steps, coating the mixed slurry on a metal beryllium sheet, and carrying out vacuum drying for 10 hours at the temperature of 100 ℃. The in-situ cell was assembled in an argon glove box with water and oxygen content less than 0.1 ppm. The in situ test was performed at a current density of 20mA/g using a constant current charge-discharge mode. As shown in fig. 4, it can be seen that no phase change occurs during the charge and discharge processes, and the calculated volume change rate is only 0.65%.
Carrying out air and water aging treatment on the layered oxide material, wherein the air aging conditions are as follows: standing in air for 10 days and 30 days; the aging condition in water is that the mixture is stirred in deionized water for 1 hour, and as a result, XRD still shows a P2 phase structure and the material structure is not changed as shown in figures 5 and 6; the electrochemical test procedure was the same as for the unaged layered oxide, and the results showed almost no degradation in electrochemical performance.
Example 2
The specific preparation process and experimental conditions were the same as in example 1, except that the magnesium oxide in the precursor oxide was replaced by zinc oxide to obtain a black powder, and the layered oxide positive electrode material was Na 0.75 Zn 0.05 [Li 0.15 Ni 0.1 Mn 0.7 ]O 2 . The XRD pattern is shown in figure 1, and from the XRD result, the material is a P2 type layered oxide, zn enters a sodium layer, and Li enters a transition metal layer.
The prepared layered oxide is used as a positive active substance for preparing and testing a sodium ion battery, the preparation process and the electrochemical test method of a positive pole piece are the same as those of the embodiment 1, the test result is shown in figure 7, after Mg is replaced by Zn, the layered oxide also has excellent electrochemical performance, and the reversible capacity reaches 140mAh g -1 (ii) a Long cycle results are shown in FIG. 3 at 0.1mAg -1 The capacity retention rate after 150 cycles under the current density is 91.5 percent.
Example 3
The preparation process and experimental conditions were the same as in example 1, but the stoichiometric ratios of anhydrous sodium carbonate, magnesium oxide, lithium hydroxide monohydrate, nickel oxide and manganese dioxide in the precursor compound were different, and black powders were obtainedThe anode material of the layered oxide is Na 0.75 Mg 0.1 [Li 0.15 Ni 0.05 Mn 0.7 ]O 2 . The XRD pattern is shown in figure 1, and from the XRD result, the material is a P2 type layered oxide, mg enters a sodium layer, and Li enters a transition metal layer.
COMPARATIVE EXAMPLE 1 (not in accordance with the invention)
The specific preparation process and experimental conditions were the same as in example 1, but the stoichiometric ratios of anhydrous sodium carbonate, lithium hydroxide monohydrate, nickel oxide, and manganese dioxide in the precursor compound were different, and the layered oxide material of the obtained black powder was Na 0.75 Li 0.15 Ni 0.15 Mn 0.7 O 2 . The XRD pattern is shown in figure 1, and the material is a P2 type layered oxide from the XRD result.
The layered oxide prepared by the method is used as a positive electrode active substance for preparing and testing a sodium ion battery, the preparation process and the electrochemical test method of the electrode plate are the same as those of the embodiment 1, the test results are shown in a figure 3 and a figure 8, and compared with the embodiment 1, the cycle performance and the rate performance are reduced, and the material structure is unstable.
COMPARATIVE EXAMPLE 2 (not in accordance with the invention)
The specific preparation process and experimental conditions were the same as in example 1, but the stoichiometric ratios of anhydrous sodium carbonate, magnesium oxide, nickel oxide, and manganese dioxide in the precursor compound were different, and the layered oxide material of black powder was obtained as Na 0.75 Mg 0.05 [Ni 0.25 Mn 0.7 ]O 2 . The XRD pattern is shown in figure 1, and the material is a P2 type layered oxide from the XRD result.
The layered oxide prepared by the method is used for preparing and testing a sodium ion battery as a positive active substance, the preparation process and the electrochemical testing method of a positive pole piece are the same as those of the embodiment 1, the testing results are shown in fig. 3 and 9, and compared with the embodiment 1, the cycle and rate performance are reduced, and the material structure is unstable.
COMPARATIVE EXAMPLE 3 (not in accordance with the invention)
The specific preparation process and experimental conditions are the same as those in example 1, but the stoichiometric ratios of anhydrous sodium carbonate, nickel oxide and manganese dioxide in the precursor compound are different,the layered oxide material of the obtained black powder was Na 0.75 Ni 0.3 Mn 0.7 O 2 . The XRD pattern is shown in figure 1, and the material is a P2 type layered oxide from the XRD result.
The layered oxide prepared by the method is used as a positive active material for preparing and testing a sodium ion battery, the preparation process and the electrochemical test method of the positive pole piece are the same as those in example 1, and the test result is shown in fig. 3 and fig. 10, so that a sample without Mg and Li doping has a large voltage platform at more than 4.2V, which corresponds to a P2-O2 phase change process, and the 150-time cycle capacity retention rate is only 64.3% under the 1C multiplying power.
COMPARATIVE EXAMPLE 4 (not in accordance with the invention)
The specific preparation process and experimental conditions were the same as in example 1, but the stoichiometric ratios of anhydrous sodium carbonate, magnesium oxide, lithium hydroxide monohydrate, nickel oxide, and manganese dioxide in the precursor compound were different, and the layered oxide material of the obtained black powder was Na 0.75 Li 0.03 Mg 0.15 Ni 0.18 Mn 0.64 O 2 . The charge and discharge results are shown in FIG. 11, and the electrochemical performance is rather deteriorated as the Mg content is increased in the example 1.
COMPARATIVE EXAMPLE 5 (not in accordance with the invention)
The specific preparation process and experimental conditions were the same as in example 1, but the stoichiometric ratios of anhydrous sodium carbonate, magnesium oxide, nickel oxide, and manganese dioxide in the precursor compound were different, and the layered oxide material of black powder was obtained as Na 0.8 Mg 0.15 Ni 0.25 Mn 0.6 O 2 . The charging and discharging results are shown in fig. 12, the first cycle charging curve has more voltage steps and plateaus, and the stability is poor.
Claims (6)
1. A layered oxide positive electrode material with low volume change in the charge and discharge processes is characterized in that: has a chemical general formula of Na x M a [M b Ni c Mn d ]O 2 ；
Wherein Ni and Mn are transition metal elements, M a And M b Metal element substituted by Na layer and transition metal layer respectivelyElement, M a Is Mg 2+ 、Ca 2+ And Zn 2+ One or more elements of (a), M b Is Li + 、Al 3+ 、K + 、Ti 4+ 、V 3+ 、Cr 5+ 、Fe 3+ 、Co 3+ And Cu 2+ X, a, b, c and d are respectively the molar ratio of the corresponding elements, x is more than or equal to 0.67 and less than or equal to 0.85, a is more than or equal to 0.03 and less than or equal to 0.1, b is more than or equal to 0.05 and less than or equal to 0.3, b + c + d is more than or equal to 0.9 and less than or equal to 1, c is more than or equal to 0.03 and less than or equal to 0.3, and d is more than or equal to 0.6 and less than or equal to 0.7; each component satisfies charge conservation and stoichiometric conservation.
2. A layered oxide positive electrode material with low volume change in the charge and discharge processes is characterized in that: the molar ratio Mb/Ma is 1.5-3.
3. A method for producing the layered oxide positive electrode material according to claim 1, characterized in that: the method comprises the following steps: will M b Mixing the oxide, carbonate, hydroxide or nitrate with a sodium source, and calcining to obtain a primary product; reacting the primary product with M a Mixing the oxide, carbonate, hydroxide, nitrate or acetate, and calcining for the second time to obtain a layered oxide cathode material; or mixing M a Of an oxide, carbonate, hydroxide or nitrate of, M b The oxide, carbonate, hydroxide, nitrate or acetate is mixed with a sodium source and calcined to obtain the layered oxide cathode material.
4. The method for producing a layered oxide positive electrode material according to claim 2, characterized in that: the calcining temperature is 850-1000 ℃, and the calcining time is 8-24 h.
5. The utility model provides a positive pole piece of sodium ion secondary battery which characterized in that: comprising the layered oxide positive electrode material according to claim 1.
6. A sodium ion secondary battery characterized in that: comprising the positive electrode sheet of claim 5.
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