CN114005969A - Metal ion doped modified sodium ion material and preparation method and application thereof - Google Patents
Metal ion doped modified sodium ion material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a metal ion doped modified sodium ion material and a preparation method and application thereof. The modified sodium ion material is prepared by doping metal ions into a crystal structure of the sodium ion material, the modified sodium ion material is of a layered structure, and the interlayer spacing of the layered structure is increased after the metal ions are doped; the general formula of the sodium ion material is NaNixFeyMnzO2Wherein x + y + z is 1. The invention successfully dopes metal ions into crystal lattices and has no influence on the original crystal structure of the anode material, thereby obtaining the batteryThe cycle performance and the capacity of the device are remarkably improved.
Description
Technical Field
The application belongs to the technical field of sodium ion batteries, and relates to a metal ion doped modified sodium ion material, and a preparation method and application thereof.
Background
With the problem of lithium source shortage becoming more serious, the application of sodium ion batteries with low price and similar working mechanism to replace lithium batteries gradually is a research hotspot in the current battery industry. The sodium mineral resources on the earth are very rich, so that the sodium ion battery can achieve lower cost, is beneficial supplement for the lithium ion battery, has great potential for large-scale application, and has important strategic significance for national economy.
Among positive electrode materials of sodium ion batteries, O3-type layered oxides have attracted much attention because they have more sodium storage sites and higher capacity. However, the layered oxide NaTMO2In Na+ 
cause-to-Li ratio during de-intercalation+ 
Larger ionic radii are prone to structural collapse over long cycles and the Jahn-Teller effect-Mn-due to the manganese site of the transition metal4+→Mn3+The conversion of (2) can deteriorate the cycle performance of the sodium ion positive electrode material.
Chinese patent publication No. CN 112510190 a discloses a P2 phase positive electrode material with a Zn ion doped to replace a nickel source and a preparation method thereof. The preparation method is simple, but is not suitable for large-scale industrial production. Secondly, in the layered sodium-ion battery cathode material, the two types of the O3 phase and the P2 phase which have completely different crystal structure differences are mainly classified. O and Na in the O3 phase are octahedral coordination, and the stacking mode of the structure is ABCABC stacking, while the P2 phase is triangular prism coordination, and the stacking mode is ABBA stacking. This results in O3 phase having a smaller interlayer spacing than P2 phase, making sodium diffusion more difficult.
Disclosure of Invention
In view of the above problems, the present invention provides a metal ion doped modified sodium ion positive electrode material, and a preparation method and an application thereof.
The invention provides a modified sodium ion anode material, which is prepared by doping metal ions into a crystal structure of the sodium ion anode material, wherein the modified sodium ion anode material is of a layered structure, and the interlayer spacing of the layered structure is increased after the metal ions are doped;
the general formula of the sodium ion anode material is NaNixFeyMnzO2Wherein x + y + z is 1; for example, x, y, z, 1/3.
Preferably, the metal ions are selected from Zn ions and/or Ca ions.
According to an embodiment of the present invention, the Zn ions occupy transition metal sites by substituting manganese in the material, making the interlayer spacing of the layered structure large.
Preferably, the molar ratio of Zn ions to sodium elements is a:1, 0.01. ltoreq. a.ltoreq.0.1, for example 2:100 or 5: 100.
According to an embodiment of the present invention, the Ca ion substitutes for a sodium site in the crystal structure, making the interlayer distance of the layered structure large.
Preferably, the molar ratio of Ca ions to sodium elements is b (1-2b), 0.01. ltoreq. b.ltoreq.0.1, for example 5:95 or 10: 90.
According to an embodiment of the present invention, the modified sodium ion material has the general formula of NaNixFeyMnz-aZnaO2Or Na1- 2bCabNixFeyMnzO2Wherein x + y + z is 1, 0.01. ltoreq. a.ltoreq.0.1, 0.01. ltoreq. b.ltoreq.0.1, preferably 0.02. ltoreq. a.ltoreq.0.05, 0.05. ltoreq. b.ltoreq.0.1. For example, a is 0.02, 0.05; b is 0.05 or 0.1.
Illustratively, the modified sodium ion material is NaNi1/3Fe1/3Mn0.31Zn0.02O2、NaNi1/3Fe1/ 3Mn0.31Zn0.05O2、Na0.9Ca0.05Ni1/3Fe1/3Mn1/3O2Or Na0.8Ca0.1Ni1/3Fe1/3Mn1/3O2。
According to an embodiment of the present invention, the metal ions are successfully doped into the interior of the material without affecting the crystal structure of the material.
The invention also provides a preparation method of the modified sodium ion material, and the preparation method is a spray drying method.
According to an embodiment of the present invention, the preparation method specifically comprises:
(1) preparing a mixed solution containing metal elements such as Na, Zn, Fe, Mn, Ni, Ca and the like with required stoichiometric quantity;
(2) carrying out spray drying on the mixed solution obtained in the step (1) to obtain a precursor;
(3) and (3) sintering the precursor in the step (2) to obtain the modified sodium ion material.
According to an embodiment of the present invention, in the step (1), the mixed solution is selected from an aqueous solution system.
According to an embodiment of the invention, in step (1), the Na is provided by a sodium salt. Preferably, the sodium salt is selected from sodium acetate or hydrate thereof, carbonate.
According to an embodiment of the invention, in step (1), the Zn is provided by a zinc salt. Preferably, the zinc salt is selected from at least one of zinc acetate or a hydrate thereof, zinc nitrate or a hydrate thereof, and zinc carbonate.
According to an embodiment of the invention, in step (1), the Ca is provided by a calcium salt. Preferably, the calcium salt is selected from at least one of an acetate salt of calcium or a hydrate thereof, a nitrate salt or a hydrate thereof.
According to an embodiment of the invention, in step (1), the Fe is provided by an iron salt. Preferably, the iron salt is selected from at least one of iron acetate or hydrate thereof, nitrate or hydrate thereof.
According to an embodiment of the invention, in step (1), the Mn is provided by a manganese salt. Preferably, the manganese salt is selected from at least one of manganese acetate or a hydrate thereof, nitrate or a hydrate thereof.
According to an embodiment of the invention, in step (1), the Ni is provided by a nickel salt. Preferably, the nickel salt is selected from at least one of an acetate salt of nickel and a hydrate thereof, a nitrate salt of nickel and a hydrate thereof.
According to an embodiment of the present invention, in step (1), the mixed solution is continuously stirred under an oil bath at 30-50 ℃ until it is clear and transparent. Preferably, the oil bath temperature is 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃ or a range selected between any two of the foregoing values.
According to an embodiment of the present invention, in the step (1), the solid content of the mixed solution is 7 wt% to 15 wt%, preferably 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt% or a range between any two of the above values. Preferably, the solid content of the mixed solution is 7 wt%.
According to the embodiment of the present invention, in the step (2), the spray drying temperature is 100-.
According to an embodiment of the invention, in step (2), the spray drying is carried out in a sprayer. The sprayer is not particularly limited in the invention, so as to realize spray drying. Preferably, the speed of the peristaltic pump of the sprayer is between 5 and 10rpm, for example 5 rpm.
According to an embodiment of the present invention, in the step (3), the sintering employs two-stage sintering, including one-stage sintering and two-stage sintering.
Preferably, the primary sintering temperature is selected from 500 ℃ to 600 ℃, and the sintering time is 4-5 h. More preferably, the first sintering temperature is selected from 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃ or a range between any two of the above values.
Preferably, the second-stage sintering temperature is selected from 870-900 ℃, and the sintering time is 15-18 h. More preferably, the second stage sintering temperature is selected from 870 ℃, 880 ℃, 890 ℃, 900 ℃ or a range between any two of the foregoing values.
Illustratively, the first stage sintering conditions are 550 ℃ sintering for 4 hours, and the second stage sintering conditions are 870 ℃ sintering for 15 hours.
Preferably, the temperature rise rate of the sintering is 1-5 deg.C/min, such as 3 deg.C/min.
According to an embodiment of the invention, in step (3), the sintering is performed in a muffle furnace.
According to an embodiment of the present invention, in the step (3), the sintering is performed under an air atmosphere.
The invention also provides application of the modified sodium ion material as a positive electrode material, preferably as a positive electrode material of a sodium ion battery.
The invention also provides a positive electrode material containing the modified sodium ion material.
The invention also provides application of the modified sodium ion material or the positive electrode material in a sodium ion battery.
The invention also provides a positive pole piece which comprises the positive pole material.
Preferably, the positive electrode plate comprises a current collector, a conductive agent coated on the current collector, an adhesive and the positive electrode material.
According to an embodiment of the present invention, the current collector is selected from any one of aluminum foil, nickel mesh, titanium mesh, stainless steel mesh, and nickel foam.
According to an embodiment of the present invention, the conductive additive is selected from at least one of carbon black, graphite powder, carbon nanotubes or graphene.
According to an embodiment of the invention, the binder is selected from at least one of polyvinylidene fluoride PVDF, polytetrafluoroethylene PTFE, sodium alginate, sodium carboxymethylcellulose CMC, styrene butadiene rubber SBR.
The invention also provides application of the positive pole piece in a sodium-ion battery.
The invention also provides a sodium ion battery which comprises the positive electrode material or the positive electrode piece.
Advantageous effects
The inventor finds that sodium ions with large radius are extracted and inserted for a long time in the continuous circulation process of the battery to cause the interior of the positive electrode materialCollapse of structure, and Mn4+To Mn3+The adverse distortion of (2) may affect Mn4+The role of the ions in maintaining stability during cycling of the cell. The inactive metal ions with larger radius and lower valence are successfully doped into the crystal structure of the anode material without any influence on the crystal structure, so that the structural stability is maintained, and the cycle stability and the capacity of the anode material can be remarkably improved. For example, partial substitution of manganese with zinc ions can suppress Mn not only to some extent by charge balancing charge neutrality4+To Mn3+The distortion of the transition metal layer can also increase the interlayer spacing of the transition metal layer, and is beneficial to the diffusion and transmission of sodium ions, thereby improving the cycle performance and the capacity of the battery; for example, calcium ions with large ionic radius are adopted to replace sodium, so that the interlayer spacing of a sodium layer is increased, the diffusion capacity of sodium ions is improved, the stability of a circulating structure is maintained, and the circulating performance of the material is obviously improved.
An XRD (X-ray diffraction) spectrum shows that after the anode material is doped with metal ions, the crystal structure of the original anode material is not damaged, and any impurity phase is not detected. Second, the overall left shift of the bi-dominant peak also indicates successful incorporation of the metal ion into the lattice. In the XRD pattern, the left shift of the two main peaks is due to the larger radius of the doped metal ion (e.g., the radius of zinc ion is larger than that of manganese ion). Electrochemical tests such as a charge-discharge curve and 1C 150-cycle circulation also show that the metal ion doping is beneficial to improving the performance of the battery in multiple aspects.
The invention successfully dopes metal ions into crystal lattices, has no influence on the original crystal structure of the anode material, and obviously improves the cycle performance and the capacity of the battery. For example, the cathode material of the invention maintains the crystal structure of the cathode material by successfully doping zinc ions, and inhibits Mn4+To Mn3+Adverse distortion of (2); the calcium ion doped anode material can replace sodium ions, enlarge the interlayer spacing of a sodium layer, improve the diffusion capacity of the sodium ions and maintain the stability of the structure in the battery cycle.
Drawings
FIG. 1a is a first-pass charge-discharge curve of a battery of comparative example and examples 1-2;
FIG. 1b is a first cycle charge and discharge curve at 0.2C for comparative example and examples 3-4;
FIG. 2a is a plot of specific discharge capacity over 150 cycles of 1C cycling for comparative example and example 1-2 battery samples;
FIG. 2b is a graph of specific discharge capacity at 150 cycles of 1C cycling for comparative and example 3-4 battery samples;
FIGS. 3a, 3b, 3c are XRD patterns of comparative example and examples 1-2.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Comparative example
Preparing a sodium ion material: 2.584g of anhydrous sodium acetate, 2.488g of nickel acetate tetrahydrate, 2.451g of manganese acetate tetrahydrate and 4.04g of ferric nitrate nonahydrate were placed in a beaker, and about 153ml of deionized water was added to obtain a solution with a solid content of 7 wt%. Heating and stirring the mixture at the temperature of 40 ℃ in an oil bath until the solution is clear and transparent, and then carrying out spray drying. During spray drying, the peristaltic pump speed of the sprayer is 5rpm, spraying is started when the sprayer is heated to 130 ℃, and finally the precursor is obtained. Placing the obtained precursor in a muffle furnace in air atmosphere, heating to 550 ℃ at a speed of 3 ℃/min, preserving heat for 4h to finish first-stage sintering, continuing heating to 870 ℃ at a speed of 3 ℃/min, preserving heat for 15h to finish second-stage sintering, cooling, and naturally cooling to obtain the sodium ion material NaNi1/3Fe1/3Mn1/3O2Hereinafter abbreviated as NFM-111.
Preparing a button cell: 0.2g of NFM-111, 0.025g of acetylene black and 0.025g of PVDF are dissolved in NMP solvent and uniformly mixed, coated on a 15-micron thick aluminum foil, dried by blowing air at 60 ℃ for 30 minutes, and dried in vacuum at 120 ℃ for 10 hours to obtain the NFM-111 battery positive plate for later use. The positive plate of the NFM-111 battery is made into a circular positive plate with the diameter of 1cm, a metal sodium plate is used as a battery negative electrode, 1.0M NaPF6PC, EMC 1:1 Vol% with 2.0% FEC is used as electrolyte, and the battery is assembled into a 2016 button battery in a glove box filled with argon, and the battery is marked as the NFM-111 battery.
Example 1
This example also prepares a ternary modified cathode material NaNi with Zn 2% (i.e., a ═ 0.02) by spray drying method1/3Fe1/3Mn0.31Zn0.02O2The method specifically comprises the following steps:
2.584g of anhydrous sodium acetate, 2.488g of nickel acetate tetrahydrate, 2.402g of manganese acetate tetrahydrate, 4.04g of ferric nitrate nonahydrate and 0.044g of zinc acetate dihydrate were placed in a beaker, and about 153ml of deionized water was added to obtain a solution with a solid content of 7 wt%. Heating and stirring the mixture at the temperature of 40 ℃ in an oil bath until the solution is clear and transparent, and then carrying out spray drying. During spray drying, the peristaltic pump speed of the sprayer is 5rpm, spraying is started when the sprayer is heated to 130 ℃, and finally the precursor is obtained. Placing the obtained precursor in a muffle furnace in air atmosphere, heating to 550 ℃ at a speed of 3 ℃/min, preserving heat for 4h to finish first-stage sintering, continuing heating to 870 ℃ at a speed of 3 ℃/min, preserving heat for 15h to finish second-stage sintering, cooling, and naturally cooling to obtain the modified sodium ion material NaNi1/3Fe1/3Mn0.31Zn0.02O2Hereinafter abbreviated as Zn-2.
Dissolving 0.2g of Zn-2, 0.025g of acetylene black and 0.025g of PVDF in an NMP solvent, uniformly mixing, coating on a 15-micron thick aluminum foil, carrying out forced air drying at 60 ℃ for 30 minutes, and carrying out vacuum drying at 120 ℃ for 10 hours to obtain a Zn-2 battery positive plate for later use. A Zn-2 battery positive plate is made into a circular positive plate with the diameter of 1cm, a metal sodium plate is used as a battery negative electrode, 1.0M NaPF6PC (electro magnetic compatibility) with EMC of 1:1 Vol% and FEC of 2.0% is used as electrolyte, and a 2016 button battery which is marked as a Zn-2 battery is assembled in a glove box filled with argon.
Example 2
This example also prepares a ternary modified cathode material NaNi with Zn 5% (i.e., a ═ 0.05) by spray drying method1/3Fe1/3Mn0.28Zn0.05O2The method specifically comprises the following steps:
2.584g of anhydrous sodium acetate, 2.488g of nickel acetate tetrahydrate, 2.328g of manganese acetate tetrahydrate, 4.04g of ferric nitrate nonahydrate and 0.11g of zinc acetate dihydrate were placed in a beaker, and about 152ml of deionized water was added to obtain a solution having a solid content of 7 wt%. Heating and stirring the mixture at the temperature of 40 ℃ in an oil bath until the solution is clear and transparent, and then carrying out spray drying. During spray drying, the peristaltic pump speed of the sprayer is 5rpm, spraying is started when the sprayer is heated to 130 ℃, and finally the precursor is obtained. Placing the obtained precursor in a muffle furnace in air atmosphere, heating to 550 ℃ at a speed of 3 ℃/min, preserving heat for 4h to finish first-stage sintering, continuing heating to 870 ℃ at a speed of 3 ℃/min, preserving heat for 15h to finish second-stage sintering, cooling, and naturally cooling to obtain the modified anode material NaNi1/3Fe1/3Mn0.28Zn0.05O2Hereinafter abbreviated as Zn-5.
0.2g of Zn-5, 0.025g of acetylene black and 0.025g of PVDF are dissolved in NMP solvent and uniformly mixed, coated on a 15-micron thick aluminum foil, dried by blowing at 60 ℃ for 30 minutes and dried in vacuum at 120 ℃ for 10 hours to obtain the Zn-5 battery positive plate for later use. A Zn-5 battery positive plate is made into a circular positive plate with the diameter of 1cm, a metal sodium plate is used as a battery negative electrode, 1.0M NaPF6PC (electro magnetic compatibility) with EMC of 1:1 Vol% and FEC of 2.0% is used as electrolyte, and a 2016 button battery which is marked as a Zn-5 battery is assembled in a glove box filled with argon.
Example 3
This example also prepares a ternary modified positive electrode material Na with a Ca 5% doping amount (i.e., b ═ 0.05) by spray drying0.9Ca0.05Ni1/3Fe1/3Mn1/3O2The method specifically comprises the following steps:
2.326g of anhydrous sodium acetate, 0.2643g of calcium acetate monohydrate, 2.488g of nickel acetate tetrahydrate, 2.451g of manganese acetate tetrahydrate and 4.04g of ferric nitrate nonahydrate were placed in a beaker, and about 153ml of deionized water was added to obtain a solution with a solid content of 7 wt%. Heating and stirring the mixture at the temperature of 40 ℃ in an oil bath until the solution is clear and transparent, and then carrying out spray drying. During spray drying, the peristaltic pump speed of the sprayer is 5rpm, spraying is started when the sprayer is heated to 130 ℃, and finally the precursor is obtained. And (3) placing the obtained precursor in a muffle furnace under the air atmosphere, heating to 550 ℃ at a speed of 3 ℃/min, preserving heat for 4h to finish primary sintering, continuing heating to 870 ℃ at a speed of 3 ℃/min, preserving heat for 15h to finish secondary sintering, cooling, and naturally cooling to obtain the modified anode material Ca-5.
0.2g of Ca-5, 0.025g of acetylene black and 0.025g of PVDF are dissolved in NMP solvent and uniformly mixed, coated on an aluminum foil with the thickness of 15 mu m, dried by blowing at 60 ℃ for 30 minutes and dried in vacuum at 120 ℃ for 10 hours to obtain the Ca-5 battery positive plate for later use. The Ca-5 battery positive plate is made into a circular positive plate with the diameter of 1cm, a metal sodium plate is used as a battery negative electrode, 1.0M NaPF6PC (electro magnetic compatibility) with EMC of 1:1 Vol% and FEC of 2.0% is used as electrolyte, and a 2016 button battery which is marked as a Ca-5 battery is assembled in a glove box filled with argon.
Example 4
This example also prepares a ternary modified positive electrode material Na with a Ca doping amount of 10% (i.e., b ═ 0.1) by spray drying0.8Ca0.1Ni1/3Fe1/3Mn1/3O2The method specifically comprises the following steps:
2.067g of anhydrous sodium acetate, 0.5285g of calcium acetate monohydrate, 2.488g of nickel acetate tetrahydrate, 2.451g of manganese acetate tetrahydrate and 4.04g of ferric nitrate nonahydrate were placed in a beaker, and about 153ml of deionized water was added to obtain a solution with a solid content of 7 wt%. Heating and stirring the mixture at the temperature of 40 ℃ in an oil bath until the solution is clear and transparent, and then carrying out spray drying. During spray drying, the peristaltic pump speed of the sprayer is 5rpm, spraying is started when the sprayer is heated to 130 ℃, and finally the precursor is obtained. And (3) placing the obtained precursor in a muffle furnace under the air atmosphere, heating to 550 ℃ at a speed of 3 ℃/min, preserving heat for 4h to finish primary sintering, continuing heating to 870 ℃ at a speed of 3 ℃/min, preserving heat for 15h to finish secondary sintering, cooling, and naturally cooling to obtain the modified anode material Ca-10.
0.2g of Ca-10, 0.025g of acetylene black and 0.025g of PVDF are dissolved in NMP solvent and uniformly mixed, coated on an aluminum foil with the thickness of 15 mu m, dried by blowing at 60 ℃ for 30 minutes and dried in vacuum at 120 ℃ for 10 hours to obtain the Ca-10 battery positive plate for later use. The Ca-10 battery positive plate is made into a circular positive plate with the diameter of 1cm, a metal sodium plate is used as a battery negative electrode, 1.0M NaPF6PC with EMC 1:1 Vol% and FEC 2.0% is used as an electrolyte, and the battery is assembled into a 2016 button battery in a glove box filled with argon, and the battery is marked as a Ca-10 battery.
Test example 1: electrochemical performance test
(1) First loop charge-discharge curve test of battery
And (3) testing conditions are as follows: the test voltage interval is 2-4V, and the current is 0.2C.
FIG. 1a is the first-turn charge-discharge curves of 0.2C for comparative example and examples 1-2, wherein the specific discharge capacities from high to low are Zn-5, Zn-2 and NFM-111. The doping of Zn ions is facilitated, and the specific discharge capacity of Zn-2 is much higher than that of NFM-111117.6 mAh/g under the current multiplying power of 0.2C. And with the increase of the doping capacity, the discharge specific capacity is slightly reduced, and the discharge specific capacity of the first ring of Zn-5 is 125.9mAh/g, but is higher than that of NFM-111. Therefore, the Zn ion doped and substituted modified material synthesized by the method can improve the specific discharge capacity of the raw material, and the discharge platform of about 3.0V is more gentle.
FIG. 1b shows the first-turn charge-discharge curves of 0.2C for comparative example and examples 3-4, wherein the specific discharge capacities from high to low are Ca-10, Ca-5 and NFM-111, respectively. The doping of Ca ions is facilitated, and the specific discharge capacity of Ca-5 at 0.2C multiplying current is much higher than that of NFM-111117.6 mAh/g, wherein the specific discharge capacity is 133.3 mAh/g. And with the increase of doping capacity, the discharge specific capacity is also slightly improved, and the discharge specific capacity of the first ring of Ca-10 is 142.87mAh/g, which is obviously higher than that of NFM-111. Therefore, the Ca ion doped and substituted modified material synthesized by the method can improve the specific discharge capacity of the raw material.
(2) Battery cycle performance test
And (3) testing conditions are as follows: the test voltage interval is 2-4V, and 150 circles are carried out after 2 circles of 0.2C activation and 1C circulation.
Fig. 2a is a plot of specific discharge capacity over 150 cycles of 1C cycling for comparative and example 1-2 battery samples. As shown in the figure, after 150 cycles of the NFM-111, the discharge specific capacity retention rate is 82.03%, and the discharge specific capacity is reduced to 93.1mAh/g from 113.5mAh/g of 1C cycle. After the battery sample of the embodiment 1-2 is circulated for 150 circles, the residual Zn-2 specific discharge capacity is 115mAh/g, and the relative initial 129.4mAh/g retention rate of the specific discharge capacity is 88.87%; the residual Zn-5 specific discharge capacity is 103.9mAh/g, and the relative initial 118.1mAh/g retention rate of the specific discharge capacity is 87.97%. Therefore, the Zn ion doped modified material obviously improves the cycle performance of the material while improving the first-turn capacity of the raw material.
Fig. 2b is a plot of specific discharge capacity over 150 cycles of 1C cycling for comparative and example 3-4 battery samples. As shown in the figure, after 150 cycles of the NFM-111, the discharge specific capacity retention rate is 82.03%, and the discharge specific capacity is reduced to 93.1mAh/g from 113.5mAh/g of 1C cycle. After the battery samples in the embodiments 3-4 are circulated for 150 circles, the Ca-5 discharge specific capacity is remained 114.6mAh/g, and the relative initial 128.3mAh/g retention rate of the discharge specific capacity is 89.32%; the residual Ca-10 discharge specific capacity is 120.4mAh/g, and the relative initial 134.35mAh/g retention rate of the discharge specific capacity is 89.61%. Therefore, the Ca ion doped modified material can remarkably improve the cycle performance of the material while improving the first-turn capacity of the raw material.
Test example 2: XRD test
In order to determine whether the modified cathode material prepared in example 1-2 is successfully doped into the crystal structure of the raw material NFM-111 and has an influence on the original structure, we performed XRD (model D8) tests on comparative example and example 1-2.
FIG. 3 is an XRD spectrum of comparative example and examples 1-2, and it can be seen from FIG. 3a that Zn-2 and Zn-5 doped with Zn ions have XRD spectrum 1 relative to the positive electrode material NFM-111, and no generation of hetero-phase is observed. This indicates that the doping of Zn ion will not destroy the original crystal structure of the material. Fig. 3b and 3c correspond to the two main peak spectra at 2 θ 15-17 ° and 2 θ 41-43 ° on 4a, respectively. As can be seen from FIGS. 3a and 3b, Zn-2 and Zn-5 both shift to the left with respect to the co-located crystal peak of NFM-111, and the phenomenon that the crystal peak shifts to the left with increasing doping amount becomes more significant. This indicates that Zn ions have been successfully doped into the crystal lattice due to the phenomenon that the ion radius of Zn ions is larger than that of Mn, causing the crystal peak to be shifted to the left.
The exemplary embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement and the like made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims (10)
1. The modified sodium ion material is characterized in that the modified sodium ion material is prepared by doping metal ions into a crystal structure of the sodium ion material, the modified sodium ion material is of a layered structure, and the interlayer spacing of the layered structure is increased after the metal ions are doped;
the general formula of the sodium ion material is NaNixFeyMnzO2Wherein x + y + z is 1.
2. The modified sodium ion material of claim 1, wherein the metal ions are selected from Zn ions and/or Ca ions.
Preferably, the Zn ion enlarges the interlayer spacing of the layered structure by occupying a transition metal site in the crystal structure.
Preferably, the molar ratio of Zn ions to sodium elements is a:1, 0.01. ltoreq. a.ltoreq.0.1, for example 2:100 or 5: 100.
Preferably, the Ca ions replace sodium sites in the crystal structure, making the interlayer spacing of the layered structure large.
Preferably, the molar ratio of the Ca ions to the sodium elements is b (1-2b), and b is more than or equal to 0.01 and less than or equal to 0.1.
Preferably, the general formula of the modified sodium ion material is NaNixFeyMnz-aZnaO2Or Na1-2bCabNixFeyMnzO2Wherein x + y + z is 1, 0.01. ltoreq. a.ltoreq.0.1, 0.01. ltoreq. b.ltoreq.0.1, preferably 0.02. ltoreq. a.ltoreq.0.05, 0.05. ltoreq. b.ltoreq.0.1.
Preferably, the metal ions are successfully doped into the material without affecting the crystal structure of the material.
3. The method of claim 1 or 2, wherein the method is a spray drying method.
Preferably, the preparation method specifically comprises:
(1) preparing a mixed solution containing metal elements such as Na, Zn, Fe, Mn, Ni, Ca and the like with required stoichiometric quantity;
(2) carrying out spray drying on the mixed solution obtained in the step (1) to obtain a precursor;
(3) and (3) sintering the precursor in the step (2) to obtain the modified sodium ion material.
4. The method according to claim 3, wherein in the step (1), the mixed solution is selected from aqueous solution systems.
Preferably, in step (1), the Na is provided by a sodium salt. Preferably, the sodium salt is selected from sodium acetate or hydrate thereof, carbonate.
Preferably, in step (1), the Zn is provided by a zinc salt. Preferably, the zinc salt is selected from at least one of zinc acetate or a hydrate thereof, and zinc nitrate or a hydrate thereof.
Preferably, in step (1), the Ca is provided by a calcium salt. Preferably, the calcium salt is selected from at least one of an acetate salt or a hydrate thereof, a nitrate salt or a hydrate thereof, and a carbonate salt of calcium.
Preferably, in step (1), the Fe is provided by an iron salt. Preferably, the iron salt is selected from at least one of iron acetate or hydrate thereof, nitrate or hydrate thereof.
Preferably, in step (1), the Mn is provided by a manganese salt. Preferably, the manganese salt is selected from at least one of manganese acetate or a hydrate thereof, nitrate or a hydrate thereof.
Preferably, in step (1), the Ni is provided by a nickel salt. Preferably, the nickel salt is selected from at least one of an acetate salt of nickel and a hydrate thereof, a nitrate salt of nickel and a hydrate thereof.
Preferably, in the step (1), the mixed solution is continuously stirred under an oil bath at the temperature of 30-50 ℃ until the mixed solution is clear and transparent. Preferably, the oil bath temperature is 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃ or a range selected between any two of the foregoing values.
Preferably, in step (1), the solid content of the mixed solution is 7 wt% to 15 wt%, preferably 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt% or a range between any two of the above values.
Preferably, in the step (2), the spray drying temperature is 100-.
Preferably, in step (2), the spray drying is carried out in a sprayer. Preferably, the speed of the peristaltic pump of the sprayer is between 5 and 10rpm, for example 5 rpm.
Preferably, in the step (3), the sintering adopts two-stage sintering, including one-stage sintering and two-stage sintering.
Preferably, the primary sintering temperature is selected from 500 ℃ to 600 ℃, and the sintering time is 4-5 h. More preferably, the first sintering temperature is selected from 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃ or a range between any two of the above values.
Preferably, the second-stage sintering temperature is selected from 870-900 ℃, and the sintering time is 15-18 h. More preferably, the second stage sintering temperature is selected from 870 ℃, 880 ℃, 890 ℃, 900 ℃ or a range between any two of the foregoing values.
Illustratively, the first stage sintering conditions are 550 ℃ sintering for 4 hours, and the second stage sintering conditions are 870 ℃ sintering for 15 hours.
Preferably, the heating rate of the sintering is 1-5 ℃/min.
Preferably, in step (3), the sintering is performed in a muffle furnace.
Preferably, in the step (3), the sintering is performed under an air atmosphere.
5. Use of the modified sodium ion material of claim 1 or 2 as a positive electrode material, preferably as a positive electrode material for a sodium ion battery.
6. A positive electrode material comprising the modified sodium ion material according to claim 1 or 2.
7. Use of the modified sodium ion material of claim 1 or 2 or the positive electrode material of claim 6 in a sodium ion battery.
8. A positive electrode sheet, characterized in that it comprises the positive electrode material according to claim 6.
9. The use of the positive electrode sheet of claim 8 in a sodium ion battery.
10. A sodium ion battery comprising the positive electrode material according to claim 6 or the positive electrode sheet according to claim 8.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115172709A (en) * | 2022-07-26 | 2022-10-11 | 上海应用技术大学 | High-performance strontium-doped ternary sodium-ion battery positive electrode material and preparation method thereof |
| CN115557546A (en) * | 2022-12-06 | 2023-01-03 | 湖州超钠新能源科技有限公司 | Sodium ion positive electrode material and preparation method and application thereof |
| CN115626669A (en) * | 2022-12-20 | 2023-01-20 | 江苏正力新能电池技术有限公司 | Conversion-type material synergistically modified sodium ion battery O3 phase layered oxide positive electrode material and preparation method and application thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109873153A (en) * | 2019-04-04 | 2019-06-11 | 中南大学 | A kind of O3 type sodium-ion battery positive material and preparation method thereof |
| CN110416521A (en) * | 2019-08-01 | 2019-11-05 | 上海应用技术大学 | A kind of sodium-ion battery tertiary cathode material and preparation method thereof of magnesium doping |
| CN111463427A (en) * | 2020-04-15 | 2020-07-28 | 江南大学 | Chloride ion doped modified lithium-rich layered cathode material and preparation method thereof |
| WO2020235909A1 (en) * | 2019-05-17 | 2020-11-26 | 한양대학교 산학협력단 | Cathode active material for calcium-doped sodium secondary battery, and sodium secondary battery including same |
| CN112234200A (en) * | 2020-09-18 | 2021-01-15 | 中南大学 | O3-type layered sodium-ion battery positive electrode material and preparation method thereof |
| CN112670497A (en) * | 2019-09-27 | 2021-04-16 | 宁德时代新能源科技股份有限公司 | Positive electrode active material for sodium ion battery, battery module, battery pack, and device each made of the active material |
-
2021
- 2021-09-29 CN CN202111154973.7A patent/CN114005969B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109873153A (en) * | 2019-04-04 | 2019-06-11 | 中南大学 | A kind of O3 type sodium-ion battery positive material and preparation method thereof |
| WO2020235909A1 (en) * | 2019-05-17 | 2020-11-26 | 한양대학교 산학협력단 | Cathode active material for calcium-doped sodium secondary battery, and sodium secondary battery including same |
| CN110416521A (en) * | 2019-08-01 | 2019-11-05 | 上海应用技术大学 | A kind of sodium-ion battery tertiary cathode material and preparation method thereof of magnesium doping |
| CN112670497A (en) * | 2019-09-27 | 2021-04-16 | 宁德时代新能源科技股份有限公司 | Positive electrode active material for sodium ion battery, battery module, battery pack, and device each made of the active material |
| CN111463427A (en) * | 2020-04-15 | 2020-07-28 | 江南大学 | Chloride ion doped modified lithium-rich layered cathode material and preparation method thereof |
| CN112234200A (en) * | 2020-09-18 | 2021-01-15 | 中南大学 | O3-type layered sodium-ion battery positive electrode material and preparation method thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115172709A (en) * | 2022-07-26 | 2022-10-11 | 上海应用技术大学 | High-performance strontium-doped ternary sodium-ion battery positive electrode material and preparation method thereof |
| CN115557546A (en) * | 2022-12-06 | 2023-01-03 | 湖州超钠新能源科技有限公司 | Sodium ion positive electrode material and preparation method and application thereof |
| CN115626669A (en) * | 2022-12-20 | 2023-01-20 | 江苏正力新能电池技术有限公司 | Conversion-type material synergistically modified sodium ion battery O3 phase layered oxide positive electrode material and preparation method and application thereof |
| CN115986106A (en) * | 2023-02-09 | 2023-04-18 | 广东凯金新能源科技股份有限公司 | Positive electrode material, preparation method thereof and sodium ion battery |
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| WO2024178917A1 (en) * | 2023-02-27 | 2024-09-06 | 荆门市格林美新材料有限公司 | Metal-ion-doped and sodium-lithium-aluminum-titanium-phosphate-coated sodium-ion battery positive electrode material, preparation method therefor, and use thereof |
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