CN115986110B - Sodium ion battery positive electrode material and preparation method thereof - Google Patents
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Abstract
The invention relates to the technical field of electrode materials, in particular to a sodium ion battery anode material and a preparation method thereof. The invention provides a positive electrode material of a sodium ion battery, which is of a single crystal lamellar structure, wherein the lamellar structure is O3 phase; the chemical composition general formula of the positive electrode material is as follows: na (Na) x {Ni a Zn b Mn c } 1‑ d M d O 2+β Wherein M is one or two of Nb and Ta, wherein x is more than 0.85 and less than or equal to 1.2, a+b+c=1, d is more than or equal to 0.01 and less than or equal to 0.5, a, b and c are not simultaneously 0, and the value of beta satisfies the balance of valence. The single crystal grain diameter of the positive electrode material is below 15 mu m. The monocrystal O3 phase layered metal oxide positive electrode material provided by the invention has the advantages of high crystallinity, no impurity phase, insensitivity to water and oxygen, stable structure and simple synthesis, and can be used as an energy storage type sodium ion battery positive electrode material.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a sodium ion battery anode material and a preparation method thereof.
Background
Along with the large-scale access of new energy, in order to overcome the intermittence and fluctuation of wind and light electricity, the whole power system is converting from 'source-net-charge' to 'source-net-charge-storage', and the energy storage becomes the fourth main element of the novel power system.
The abundance of lithium element is low, the crust abundance is only 0.006%, most of the lithium element is concentrated in south america, and the price of the lithium raw material is continuously increased in 2020, so that the selling price of the downstream energy storage equipment is increased suddenly. In contrast, the source of sodium element is wide, the price is low, the performance of the sodium ion battery is excellent, and the sodium ion battery has strong potential in the traffic field and the large-scale energy storage field.
The sodium ion battery using the layered metal oxide as the positive electrode material has the working principle similar to that of the lithium ion battery, and the technical development is also driven by the lithium ion battery. However, the O3-phase layered metal oxide widely used in sodium ion batteries is prone to structural phase change or phase inversion layer during the deintercalation process, which results in degradation of battery cycle performance, and the structure is sensitive to environmental water and oxygen and poor in post-processing performance. Therefore, how to solve the irreversible phase change and water oxygen sensitivity problems in the material circulation process is a key point that the low-cost sodium ion battery can be widely applied.
Disclosure of Invention
Aiming at the key technical problems of the layered metal oxide positive electrode of the sodium ion battery, one of the purposes of the invention is to provide a positive electrode material of the sodium ion battery, wherein the positive electrode material of the sodium ion battery is single-crystal O3-phase layered metal oxide, the metal oxide not only shows excellent electrochemistry of the layered metal oxide material rich in sodium, but also avoids the problems of water oxygen sensitivity and irreversible phase transformation of the material.
Specifically, the chemical composition general formula of the positive electrode material of the sodium ion battery is as follows: na (Na) x {Ni a Zn b Mn c } 1-d M d O 2+β Wherein M is one or two of Nb and Ta, wherein x is more than 0.85 and less than or equal to 1.2, a+b+c=1, d is more than or equal to 0.01 and less than or equal to 0.5, a, b and c are not simultaneously 0, and the value of beta meets the balance of valence;
the positive electrode material of the sodium ion battery is in a structure that transition metal layers and sodium layers are stacked alternately, and the transition metal layers and the sodium layers are connected through oxygen atoms;
the O3 phase is an octahedral structure composed of transition metal elements and oxygen elements, and the repeated single source is 3 stacking; the sodium ions are located in an octahedral coordination environment of oxygen, wherein M-O weak coordination structures are formed by doping manganese sites with high-valence transition metal tantalum or niobium.
The valence states of Mn in the positive electrode material include +2 valence and +3 valence.
In one specific embodiment, when x=1, a=0.8, b=0.1, c=0.1, d=0.05, and β has a value satisfying the valence balance, the positive electrode material of the sodium ion battery has a chemical formula: na { Ni 0.8 Zn 0.1 Mn 0.1 } 0.95 Ta 0.05 O 2+β Or Na { Ni 0.8 Zn 0.1 Mn 0.1 } 0.95 Nb 0.05 O 2+β 。
Preferably, the single crystal positive electrode material comprises small particles with the particle size of 10-200 nm and large particles with the particle size of 3-15 mu m.
The second purpose of the invention is to provide the preparation method of the sodium ion battery anode material, which comprises the following steps:
(1) Weighing a sodium source compound, a nickel source compound, a manganese source compound and a zinc source compound according to stoichiometric numbers, and premixing to obtain premixed powder;
(2) Grinding the premixed powder, the solvent, the niobium source compound and/or the tantalum source compound and the dispersing agent obtained in the step (1) through a nano sand mill to obtain slurry, wherein the primary particle size range of the slurry is 50-100 nm;
(3) Spray drying and granulating the slurry obtained in the step (2) to obtain a composite precursor;
(4) And (3) performing high-temperature sintering and cooling on the composite precursor obtained in the step (3) to obtain the positive electrode material.
Preferably, in the step (1), the sodium source compound comprises any one or more of sodium carbonate, sodium bicarbonate, trisodium citrate, sodium acetate and sodium oxalate; the nickel source compound comprises one or more of nickel oxide, nickel hydroxide, nickel acetate and nickel nitrate; the manganese source compound comprises any one or more of manganese oxide, manganese hydroxide, manganese acetate and manganese nitrate; the zinc source compound comprises any one or more of zinc oxide, zinc hydroxide, zinc acetate and zinc nitrate.
Preferably, in the step (2), the dispersing agent is any one or more of polyvinylpyrrolidone, cetyltrimethylammonium bromide, acetylenic diol and dodecylbenzene sulfonic acid.
Preferably, in the step (2), the solvent is any one or more of deionized water, ethanol and isopropanol.
Preferably, in the step (2), the niobium source compound is nano niobium pentoxide; the tantalum source compound is tantalum ethoxide. The primary particle size of the nano niobium pentoxide is 100-500 nm.
Preferably, in the step (3), the inlet temperature of the spray dryer used for spray drying is 150-200 ℃ and the outlet temperature is 80-100 ℃.
Preferably, in the step (4), the sintering temperature is 700-950 ℃, the heat preservation time is 8-20 h, and the heating rate from the heating to the calcining temperature is 5-10 ℃/min.
Preferably, in the step (2), the primary particle size range of the slurry ground by the nano sand mill is 50-100 nm.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a sodium ion battery anode material, which has the chemical composition general formula: na (Na) x {Ni a Zn b Mn c } 1- d M d O 2+β Wherein M is one or two of Nb and Ta, wherein x is more than 0.85 and less than or equal to 1.2, a+b+c=1, d is more than or equal to 0.01 and less than or equal to 0.5, a, b and c are not simultaneously 0, and the value of beta satisfies the balance of valence. The positive electrode material of the sodium ion battery is a structure of alternately stacking transition metal layers (-TM-) and sodium layers (-Na-) which are connected through oxygen atoms, namely the positive electrode material comprises
And->
The method comprises the steps of carrying out a first treatment on the surface of the The O3 phaseThe structure is an octahedral structure composed of transition metal elements and oxygen elements, and the repeated single source is 3 stacks; the sodium ions are located in an oxygen octahedral coordination environment, wherein a weaker M-O coordination structure is formed by doping manganese sites with high-valence transition metal tantalum or niobium, so that excellent water-oxygen tolerance and electrochemical performance are realized. The anode material is prepared by mixing transition metal elements with multiple functions, wherein nickel is taken as a main element, and is an electrochemical active element, so that high capacity is provided; zinc and manganese are cooperated to serve as structural stabilizing elements, so that cation mixing and discharging can be effectively reduced, and the material cycle reversibility is improved; the niobium and tantalum with high oxidation state are used as doping elements, so that a stronger metal-oxygen bond can be formed, and the influence of the external environment on the layered structure is effectively resisted. The electrochemical stability and the water resistance of the material can be obviously improved through the synergistic effect among a plurality of transition metal elements of nickel, zinc, manganese, niobium and tantalum. By introducing high-valence transition metal tantalum or niobium to replace Mn, irreversible phase change of O3 phase in the charge-discharge process can be effectively inhibited, so that the cycle is stable. This is due to the presence +.>
Or->
Weak complexation, which allows +.>
Expand and allow->
And (5) shrinkage. The narrower sodium interlayer spacing and the relatively widened transition metal layer will reduce cation mixing, so that water molecules are not easy to enter +.>
Layers, and exhibit excellent cycling stability. When there is no->
Or->
In the case of weak complexation, this makes +.>
Shrink and enable->
And (5) expanding. This wider sodium interlayer spacing and relatively contracted transition metal layer will cause severe cation mixing, making water molecules easier to enter +.>
Layers, therefore, are prone to phase change after humid air or water bubbles.
(2) The positive electrode material of the sodium ion battery provided by the invention can not generate phase change after being soaked in humid air or water, can not generate the phenomena of caking, gel and the like in the process of preparing and pulping electrode plates, and has excellent processing performance. Because the high valence transition metal ions have the characteristics of high charge, large ionic radius and strong self-polarization capability, the doping of niobium and tantalum can reduce the mixed discharge degree of cations in the nickel zinc sodium manganate, and simultaneously strengthen the stability of a layered structure, thereby providing larger space and diffusion speed for the deintercalation of sodium ions in crystal lattices, effectively resisting the irreversible reaction of water oxygen and sodium in the external environment, and further improving the environmental tolerance and electrochemical performance of the material.
(3) The positive electrode material of the sodium ion battery provided by the invention is single-crystal O3 phase layered metal oxide, and compared with the conventional oxide positive electrode, the positive electrode material has higher sodium content, can effectively overcome the defect of low first effect of a matched negative electrode, and has wider matching selection interval of the whole battery. Since the negative electrode material generally has the defect of low initial coulombic efficiency, more sodium is needed to compensate for the initial irreversibility of the negative electrode when the full battery is charged and discharged for the first time. The positive electrode material of the sodium ion battery provided by the invention is single crystal O3 phase layered metal oxide, is a sodium-rich phase material, and can have redundant sodium to be supplied to a negative electrode, so that the positive electrode material provided by the invention is used for manufacturing a full battery, and more negative electrode materials can be selected in a matching way.
(4) According to the preparation method of the sodium ion battery anode material, provided by the invention, the nano sand mill and spray drying are used for preparing the composite precursor, so that the doping elements are more uniform, the process is simpler, the granularity can be controlled, and the preparation method is more suitable for industrial production.
(5) The monocrystal O3 phase layered metal oxide positive electrode material provided by the invention has the advantages of high crystallinity, no impurity phase, insensitivity to water and oxygen, stable structure, simplicity in synthesis, capability of greatly improving the stability of the material, capability of ensuring excellent performance, and very wide application prospect in high-stability and large-capacity sodium ion batteries.
In addition to the objects, features and advantages described above, the present invention has other objects, features and advantages. The present invention will be described in further detail with reference to the drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is an SEM image of the positive electrode material prepared in example 1;
FIG. 2 is an XRD pattern of the positive electrode material prepared in example 1;
FIG. 3 is an XRD pattern of the positive electrode material prepared in example 1 after being immersed in water for 12 hours and exposed to air for 10 days;
fig. 4 is a charge-discharge cycle chart of a battery assembled using the positive electrode material prepared in example 1;
FIG. 5 is an SEM image of the positive electrode material prepared in example 2;
fig. 6 is a charge-discharge cycle chart of a battery assembled using the positive electrode material prepared in example 2;
fig. 7 is an SEM image of the positive electrode material prepared in example 3;
fig. 8 is a charge-discharge cycle chart of a battery assembled using the positive electrode material prepared in example 3;
fig. 9 is an SEM image of the positive electrode material prepared in comparative example 1;
fig. 10 is an XRD pattern of the positive electrode material prepared in comparative example 1;
FIG. 11 XRD pattern was performed after the positive electrode material prepared in comparative example 1 was immersed in water for 12 hours and exposed to air for 10 days;
fig. 12 is a charge-discharge cycle chart of a battery assembled using the positive electrode material prepared in comparative example 1;
fig. 13 is a charge-discharge cycle chart of a battery assembled using the positive electrode material prepared in comparative example 2;
fig. 14 is a charge-discharge cycle chart of a battery assembled using the positive electrode material prepared in comparative example 3.
Detailed Description
The invention also provides an application of the positive electrode material prepared by the technical scheme or the preparation method of the technical scheme in sodium ion batteries. The method of application of the present invention is not particularly limited, and the application of the positive electrode material in a sodium ion battery is well known to those skilled in the art.
The positive electrode material, the method of preparing the same, and the use thereof will be described in detail with reference to examples, but they should not be construed as limiting the scope of the invention.
Layered oxide (NaMO) 2 M is one or more transition metal elements or other doping elements) has been the primary positive electrode material for lithium ion batteries, which is produced by co-edge MO 6 The octahedra form repeating lamellar structures between which sodium ions are located in an oxygen Octahedral coordination environment, forming a so-called O-type (Octahedral) stacking configuration. In the process of exploring the electrode material of sodium ion battery, sodium ion layered oxide (Na x MO 2 ) Naturally becomes the primary research object. However, with LiMO 2 Tends to form O-type structure, sodium ion is in MO 6 The interlayer formed by the polyhedron has two coordination environments with oxygen, and is divided into two configurations of O and P (triangular prism), wherein O3 and P2 are two most common structures in the layered positive electrode material of the sodium ion battery (the number represents the stacking layer number of the minimum repeating unit of oxygen, for example, 2 corresponds to ABBA …, and 3 corresponds to ABCABC …).
The O3 phase being M by co-edgeO 6 The octahedra form repeating lamellar structures between which sodium ions are located in an oxygen Octahedral coordination environment, forming a so-called O-type (Octahedral) stacking configuration. However, the conventional O3 phase layered oxide belongs to a sodium-rich structure, has larger interlayer spacing and is sensitive to water and oxygen in the air. According to the invention, through the weak coordination effect formed by doping the high-valence transition metal tantalum or niobium on the manganese site, the interlayer distance is effectively reduced, the tolerance to water and oxygen is realized, and meanwhile, the atomic size of the high-valence element itself also reserves the space for effectively deintercalating sodium ions, so that the common advantages of the tolerance to water and oxygen and the electrochemical performance are realized.
The invention is illustrated below with reference to specific examples.
Example 1
The preparation method of the sodium ion battery anode material comprises the following steps:
weighing sodium carbonate, nickel hydroxide, manganese hydroxide and zinc oxide according to the molar ratio of n (Na), n (Ni), n (Zn) and n (Mn) =1:0.8:0.1:0.1, and carrying out powder pre-grinding and mixing to obtain premixed powder, wherein the excess of the sodium carbonate is 5%;
the premixed powder, tantalum ethoxide and ethanol are mixed according to m (premixed powder): m (tantalum ethoxide): m (ethanol) =100: 5:200, and adding polyvinylpyrrolidone (the polyvinylpyrrolidone is 1.5% of the ethanol consumption) into a nano sand mill for grinding, and monitoring the particle size of the slurry in real time until the primary particle size of the slurry is 80 nm;
diluting the slurry with ethanol until the solid content is 30%, and performing spray drying granulation to obtain a composite precursor, wherein the inlet temperature of a spray dryer used for spray drying is 150 ℃ and the outlet temperature is 80 ℃;
sintering the composite precursor for 8 hours at 910 ℃ in air, and naturally cooling to room temperature to obtain the positive electrode material. The chemical composition of the positive electrode material is as follows: na { Ni 0.8 Zn 0.1 Mn 0.1 } 0.95 Ta 0.05 O 2+β The method comprises the steps of carrying out a first treatment on the surface of the The valence states of Mn include +2 and +3.
SEM test is carried out on the positive electrode material, and the test result is shown in figure 1; XRD testing is carried out on the positive electrode material, and the testing result is shown in figure 2; as can be seen from fig. 1 and 2, the positive electrode material is a layered O3 phase single crystal material with a particle size of 3 to 10 μm.
After the positive electrode material was immersed in water for 12 hours, XRD test was performed after 10 days of exposure in air, and the test results are shown in fig. 3. As can be seen from fig. 3, the positive electrode material is very stable in water and air, and does not undergo phase change after soaking. The high valence transition metal ions have the characteristics of high charge, large ionic radius and strong self-polarization capability, and by doping tantalum, the mixing degree of cations in the nickel zinc sodium manganate can be reduced, and meanwhile, the stability of a layered structure is enhanced, so that a larger space and diffusion speed are provided for the deintercalation of sodium ions in a crystal lattice, the irreversible reaction of water oxygen and sodium in the external environment is effectively resisted, and the environmental tolerance and electrochemical performance of the material are improved.
Drying the positive electrode material for 12 hours at 110 ℃ under vacuum, and uniformly dispersing 8g of the dried positive electrode material, 1g of super-P and 1g of vinylidene fluoride in N-methyl-2-pyrrolidone to obtain slurry; coating the slurry on aluminum foil, vacuum drying at 120 ℃, cutting into pole pieces, and in a high-purity argon glove box, taking metal sodium as a negative electrode, glass fiber as a diaphragm and 1M NaPF 6 EC+DME (1:1) is the electrolyte supporting button cell for the test.
The battery is subjected to charge-discharge performance test (voltage range is 2.0-4.2V) under the 0.1C multiplying power, the test result is shown in figure 4, and as can be seen from figure 4, the capacity retention rate of the assembled battery after 100 cycles is 93%, and the application value of the positive electrode material is fully shown. This is because the high valence transition metal tantalum replaces the Mn site, and can effectively inhibit the irreversible phase transition of the O3 phase during charge and discharge, thus achieving stable circulation.
Example 2
The preparation method of the sodium ion battery anode material comprises the following steps:
weighing sodium carbonate, nickel hydroxide, manganese hydroxide and zinc oxide according to the molar ratio of n (Na), n (Ni), n (Zn) and n (Mn) =1:0.8:0.1:0.1, and carrying out powder pre-grinding and mixing to obtain premixed powder, wherein the excess of the sodium carbonate is 5%;
the premixed powder, niobium oxide and ethanol are mixed according to m (premixed powder): m (niobium oxide): m (ethanol) =100: 6:200, and adding polyvinylpyrrolidone (the polyvinylpyrrolidone is 1.5% of the ethanol consumption) into a nano sand mill for grinding, and monitoring the particle size of the slurry in real time until the primary particle size of the slurry is 80 nm;
diluting the slurry with ethanol until the solid content is 30%, and performing spray drying granulation to obtain a composite precursor, wherein the inlet temperature of a spray dryer used for spray drying is 180 ℃ and the outlet temperature is 90 ℃;
and sintering the composite precursor in air at 700 ℃ for 20 hours, and naturally cooling to room temperature to obtain the positive electrode material.
The chemical composition of the positive electrode material is as follows: na { Ni 0.8 Zn 0.1 Mn 0.1 } 0.95 Nb 0.05 O 2+β The method comprises the steps of carrying out a first treatment on the surface of the The valence states of Mn include +2 and +3; the positive electrode material is of a layered structure, and the layered metal oxide structure is of an O3 phase; the positive electrode material is monocrystalline macroparticles with the diameter of 3-10 mu m.
SEM test was performed on the positive electrode material prepared in example 2, and the test results are shown in fig. 5; as can be seen from fig. 5, the positive electrode material is a layered O3 phase single crystal material. Fig. 6 is a charge-discharge cycle chart of a battery assembled using the positive electrode material prepared in example 2.
Example 3
The preparation method of the sodium ion battery anode material comprises the following steps:
weighing sodium carbonate, nickel hydroxide, manganese hydroxide and zinc oxide according to the molar ratio of n (Na), n (Ni), n (Zn) and n (Mn) =1:0.8:0.1:0.1, and carrying out powder pre-grinding and mixing to obtain premixed powder, wherein the excess of the sodium carbonate is 5%;
mixing the premixed powder, niobium oxide, tantalum ethoxide and ethanol according to m (premixed powder): m (niobium oxide): m (tantalum ethoxide): m (ethanol) =100: 2.8:2.5:200, and adding polyvinylpyrrolidone (the polyvinylpyrrolidone is 1.5% of the ethanol consumption) into a nano sand mill for grinding, and monitoring the particle size of the slurry in real time until the primary particle size of the slurry is 80 nm;
diluting the slurry with ethanol until the solid content is 30%, and performing spray drying granulation to obtain a composite precursor, wherein the inlet temperature of a spray dryer used for spray drying is 200 ℃ and the outlet temperature is 100 ℃;
sintering the composite precursor in air at 950 ℃ for 8 hours, and naturally cooling to room temperature to obtain the positive electrode material.
The chemical composition of the positive electrode material is as follows: na { Ni 0.8 Zn 0.1 Mn 0.1 } 0.95 Nb 0.02 Ta 0.03 O 2+β The method comprises the steps of carrying out a first treatment on the surface of the The valence states of Mn include +2 and +3; the positive electrode material is of a layered structure, and the layered metal oxide structure is of an O3 phase; the positive electrode material is monocrystalline macroparticles with the diameter of 3-10 mu m.
SEM test was performed on the positive electrode material prepared in example 2, and the test results are shown in fig. 7; as can be seen from fig. 7, the positive electrode material is a layered O3 phase single crystal material. Fig. 8 is a charge-discharge cycle chart of a battery assembled using the positive electrode material prepared in example 3.
Comparative example 1 (free of M element)
The preparation method of the sodium ion battery anode material comprises the following steps:
weighing sodium carbonate, nickel hydroxide, manganese hydroxide and zinc oxide according to the molar ratio of n (Na), n (Ni), n (Zn) and n (Mn) =1:0.8:0.1:0.1, and carrying out powder pre-grinding and mixing to obtain premixed powder, wherein the excess of the sodium carbonate is 5%;
the premixed powder and ethanol were mixed according to m (premixed powder): m (ethanol) =100: 200, and adding polyvinylpyrrolidone (the polyvinylpyrrolidone is 1.5% of the ethanol consumption) into a nano sand mill for grinding, and monitoring the particle size of the slurry in real time until the primary particle size of the slurry is 80 nm;
diluting the slurry with ethanol until the solid content is 30%, and performing spray drying granulation to obtain a composite precursor, wherein the inlet temperature of a spray dryer used for spray drying is 150 ℃ and the outlet temperature is 80 ℃;
sintering the composite precursor for 8 hours at 910 ℃ in air, and naturally cooling to room temperature to obtain the positive electrode material.
The chemical composition of the positive electrode material is as follows: naNi 0.8 Zn 0.1 Mn 0.1 O 2+β The method comprises the steps of carrying out a first treatment on the surface of the The valence states of Mn include +2 and +3; the positive electrode material is of a layered structure, and the layered metal oxide structure is of an O3 phase; the positive electrode material is monocrystalline macroparticles with the diameter of 3-10 mu m.
SEM test was performed on the positive electrode material prepared in comparative example 1, and the test results are shown in fig. 9; XRD testing is carried out on the positive electrode material, and the testing result is shown in figure 10; as can be seen from FIGS. 9 and 10, XRD test O3 (003)/O3 (104) of comparative example 1 was much smaller than the ratio of O3 (003)/O3 (104) of example 1 (FIGS. 2 and 3), demonstrating that there is no
Or->
Weak complexation, which allows +.>
Shrink and enable->
And (5) expanding. This wider sodium interlayer spacing and relatively contracted transition metal layer will cause severe cation mixing and make water molecules more accessible +.>
A layer.
The positive electrode material prepared in comparative example 1 was immersed in water for 12 hours, and then exposed to air for 10 days for XRD test, and the test results are shown in fig. 11. As can be seen from fig. 11, the positive electrode material is unstable in water and air, and undergoes a phase change after soaking. This is because sodium ions in the crystal lattice are not soluble in the ambient water oxygen and thus undergo an irreversible phase change.
Fig. 12 is a charge-discharge cycle chart of a battery assembled using the positive electrode material prepared in comparative example 1.
Comparative example 2 (M element content is too high)
The preparation method of the sodium ion battery anode material comprises the following steps:
weighing sodium carbonate, nickel hydroxide, manganese hydroxide and zinc oxide according to the molar ratio of n (Na), n (Ni), n (Zn) and n (Mn) =1:0.8:0.1:0.1, and carrying out powder pre-grinding and mixing to obtain premixed powder, wherein the excess of the sodium carbonate is 5%;
the premixed powder, tantalum ethoxide and ethanol are mixed according to m (premixed powder): m (tantalum ethoxide): m (ethanol) =100: 55:200, and adding polyvinylpyrrolidone (the polyvinylpyrrolidone is 1.5% of the ethanol consumption) into a nano sand mill for grinding, and monitoring the particle size of the slurry in real time until the primary particle size of the slurry is 80 nm;
diluting the slurry with ethanol until the solid content is 30%, and performing spray drying granulation to obtain a composite precursor, wherein the inlet temperature of a spray dryer used for spray drying is 150 ℃ and the outlet temperature is 80 ℃;
sintering the composite precursor for 8 hours at 910 ℃ in air, and naturally cooling to room temperature to obtain the positive electrode material.
The chemical composition of the positive electrode material is as follows: na { Ni 0.8 Zn 0.1 Mn 0.1 } 0.4 Ta 0.6 O 2+β The method comprises the steps of carrying out a first treatment on the surface of the The valence states of Mn include +2 and +3; the positive electrode material is of a layered structure, and the layered metal oxide structure is of an O3 phase; the positive electrode material is monocrystalline macroparticles with the diameter of 3-10 mu m. Fig. 13 is a charge-discharge cycle chart of a battery assembled using the positive electrode material prepared in comparative example 2.
Comparative example 3 (M element content is too low)
The preparation method of the sodium ion battery anode material comprises the following steps:
weighing sodium carbonate, nickel hydroxide, manganese hydroxide and zinc oxide according to the molar ratio of n (Na), n (Ni), n (Zn) and n (Mn) =1:0.8:0.1:0.1, and carrying out powder pre-grinding and mixing to obtain premixed powder, wherein the excess of the sodium carbonate is 5%;
the premixed powder, tantalum ethoxide and ethanol are mixed according to m (premixed powder): m (tantalum ethoxide): m (ethanol) =100: 0.5:200, and adding polyvinylpyrrolidone (the polyvinylpyrrolidone is 1.5% of the ethanol consumption) into a nano sand mill for grinding, and monitoring the particle size of the slurry in real time until the primary particle size of the slurry is 80 nm;
diluting the slurry with ethanol until the solid content is 30%, and performing spray drying granulation to obtain a composite precursor, wherein the inlet temperature of a spray dryer used for spray drying is 150 ℃ and the outlet temperature is 80 ℃;
sintering the composite precursor for 8 hours at 910 ℃ in air, and naturally cooling to room temperature to obtain the positive electrode material.
The chemical composition of the positive electrode material is as follows: na { Ni 0.8 Zn 0.1 Mn 0.1 } 0.995 Ta 0.005 O 2+β The method comprises the steps of carrying out a first treatment on the surface of the The valence states of Mn include +2 and +3; the positive electrode material is of a layered structure, and the layered metal oxide structure is of an O3 phase; the positive electrode material is monocrystalline macroparticles with the diameter of 3-10 mu m. Fig. 14 is a charge-discharge cycle chart of a battery assembled using the positive electrode material prepared in comparative example 3.
Drying the positive electrode materials prepared in examples 1-3 and comparative examples 1-3 at 110 ℃ for 12 hours under vacuum, and uniformly dispersing 8g of the dried positive electrode material, 1g of super-P and 1g of vinylidene fluoride in N-methyl-2-pyrrolidone to obtain slurry; coating the slurry on an aluminum foil, vacuum drying at 120 ℃, cutting into pole pieces, and in a high-purity argon glove box, taking metal sodium as a negative electrode, glass fiber as a diaphragm and 1MNAPF 6 EC+DME (1:1) is the electrolyte supporting button cell for the test.
The batteries assembled from the positive electrode materials prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to a charge-discharge performance test (voltage range of 2.0 to 4.2 v) at a 0.1C rate, and the experimental results are shown in table 1.
TABLE 1
As is clear from Table 1, comparison between example 1 and comparative example 1 shows thatThe batteries assembled by the positive electrode materials prepared in example 1 and comparative example 1 were subjected to a charge-discharge performance test at a 0.1C rate, and the initial discharge specific capacities were 148.5mAh/g and 141.7mAh/g, respectively, and the initial charge-discharge efficiencies were 94.5% and 90.1%, respectively, which were not very different. After the positive electrode materials prepared in example 1 and comparative example 1 were immersed in water for 12 hours and exposed to air for 10 days, the first discharge specific capacities were 147.7mAh/g and 101.2mAh/g, respectively, and the first charge and discharge efficiencies were 94.1% and 79.5%, respectively, which gave a significant difference. This is because there is no comparative example 1
Or->
Weak complexation, which allows +.>
Shrink and enable->
And (5) expanding. This wider sodium interlayer spacing and relatively contracted transition metal layer will cause severe cation mixing, making water molecules easier to enter +.>
The layers, therefore, comparative example 1 exhibited lower first-effect and cycle performance. However, the introduction of an excessive amount of inactive element directly resulted in a lower reversible capacity of comparative example 2. Although comparative example 3 incorporated Ta, the lower content did not give rise to improved material properties. In contrast, examples 1-3 with the appropriate amount of doping were due to the presence
Or->
Weak complexation, which allows +.>
Expand and allow->
And (5) shrinkage. This narrower sodium interlayer spacing and relatively broader transition metal layer will lead to reduced cation mixing, so that water molecules do not easily enter +.>
Layers, and exhibit excellent cycling stability. Although the example 1 material was immersed in water and exposed to humid air, its initial capacity and efficiency of electricity to be powered did not decay.
In conclusion, the positive electrode material of the sodium ion battery provided by the invention can not generate phase change after being soaked in humid air or water, can not generate phenomena such as caking, gel and the like in the process of preparing and pulping electrode plates, and has excellent processability. Because the high valence transition metal ions have the characteristics of high charge, large ionic radius and strong self-polarization capability, the doping of niobium and tantalum can reduce the mixed discharge degree of cations in the nickel zinc sodium manganate, and simultaneously strengthen the stability of a layered structure, thereby providing larger space and diffusion speed for the deintercalation of sodium ions in crystal lattices, effectively resisting the irreversible reaction of water oxygen and sodium in the external environment, and further improving the environmental tolerance and electrochemical performance of the material. The monocrystal O3 phase layered metal oxide positive electrode material provided by the invention has the advantages of high crystallinity, no impurity phase, insensitivity to water and oxygen, stable structure, simplicity in synthesis, capability of greatly improving the stability of the material, capability of ensuring excellent performance, and very wide application prospect in high-stability and large-capacity sodium ion batteries. In addition, the preparation method of the sodium ion battery anode material provided by the invention prepares the composite precursor by using the combination of the nano sand mill and spray drying, so that the doping element is more uniform, the process is simpler, the granularity can be controlled, and the preparation method is more suitable for industrial production.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The preparation method of the sodium ion battery anode material is characterized in that the sodium ion battery anode material is of a single crystal lamellar structure, and the lamellar structure is O3 phase;
the chemical composition general formula of the positive electrode material of the sodium ion battery is as follows: na (Na) x {Ni a Zn b Mn c } 1-d M d O 2+β Wherein M is one or two of Nb and Ta, wherein x is more than 0.85 and less than or equal to 1.2, a+b+c=1, d is more than or equal to 0.01 and less than or equal to 0.5, a, b and c are not simultaneously 0, and the value of beta meets the balance of valence;
the positive electrode material of the sodium ion battery is in a structure that transition metal layers and sodium layers are stacked alternately, and the transition metal layers and the sodium layers are connected through oxygen atoms;
the O3 phase is an octahedral structure composed of transition metal elements and oxygen elements, and the repeated single source is 3 stacking; the sodium ions are located in an octahedral coordination environment of oxygen, wherein M-O weak coordination structure is formed by doping manganese sites with high-valence transition metal tantalum or niobium;
the preparation method comprises the following steps:
(1) Weighing a sodium source compound, a nickel source compound, a manganese source compound and a zinc source compound according to stoichiometric numbers, and premixing to obtain premixed powder;
(2) Grinding the premixed powder, the solvent, the niobium source compound and/or the tantalum source compound and the dispersing agent obtained in the step (1) through a nano sand mill to obtain slurry;
(3) Spray drying and granulating the slurry obtained in the step (2) to obtain a composite precursor;
(4) And (3) performing high-temperature sintering and cooling on the composite precursor obtained in the step (3) to obtain the positive electrode material.
2. The method of preparing a positive electrode material for sodium ion batteries according to claim 1, wherein in the step (1), the sodium source compound comprises any one or more of sodium carbonate, sodium bicarbonate, trisodium citrate, sodium acetate, and sodium oxalate; the nickel source compound comprises any one or more of nickel oxide, nickel hydroxide, nickel acetate and nickel nitrate; the manganese source compound comprises any one or more of manganese oxide, manganese hydroxide, manganese acetate and manganese nitrate; the zinc source compound comprises any one or more of zinc oxide, zinc hydroxide, zinc acetate and zinc nitrate.
3. The method for preparing a positive electrode material of a sodium ion battery according to claim 1, wherein in the step (2), the niobium source compound is nano niobium pentoxide; the primary particle size of the nano niobium pentoxide is 100-500 nm; the tantalum source compound is tantalum ethoxide.
4. The method for preparing a positive electrode material of a sodium ion battery according to claim 1, wherein in the step (2), the dispersing agent is any one or more of polyvinylpyrrolidone, cetyltrimethylammonium bromide, acetylenic diol, dodecylbenzenesulfonic acid; the solvent is any one or more of deionized water, ethanol and isopropanol.
5. The method for preparing a positive electrode material for sodium ion battery according to claim 1, wherein in the step (3), the spray dryer used for spray drying has an inlet temperature of 150 to 200 ℃ and an outlet temperature of 80 to 100 ℃.
6. The method for preparing a positive electrode material of a sodium ion battery according to claim 1, wherein in the step (4), the high-temperature sintering temperature is 700-950 ℃, the heat preservation time is 8-20 h, and the heating rate for heating to the high-temperature sintering temperature is 5-10 ℃/min.
7. The method for preparing a positive electrode material of a sodium ion battery according to claim 1, wherein in the step (2), the primary particle size range of the slurry ground by the nano sand mill is 50-100 nm.
8. The positive electrode material for sodium ion battery prepared by the preparation method of any one of claims 1 to 7, wherein the chemical composition formula of the positive electrode material for sodium ion battery is as follows: na (Na) x {Ni a Zn b Mn c } 1-d M d O 2+β Where x=1, a=0.8, b=0.1, c=0.1, d=0.05, and β satisfies the valence balance.
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