CN120878810A - Thermoelectric effect NbSe2Surface modified O3 type layered oxide positive electrode material and preparation method thereof - Google Patents
Thermoelectric effect NbSe2Surface modified O3 type layered oxide positive electrode material and preparation method thereofInfo
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Abstract
本发明涉及钠离子电池电极材料制备技术领域，特别涉及一种热电效应NbSe2表面改性O3型层状氧化物正极材料及其制备方法，所述NbSe2表面改性O3型层状氧化物正极材料以化学式为NaNixFeyMnzO2的钠离子电池层状氧化物正极材料为基体，其中0.2≤x≤0.4，0.2≤y≤0.4，0.2≤z≤0.4，并在所述基体的表面构建NbSe2包覆层，所述NbSe2与钠离子电池层状氧化物正极材料NaNixFeyMnzO2的质量比为1：50～200。NbSe2作为保护层稳定包覆在钠离子电池层状氧化物正极材料表面，缓解正极材料的副反应，有效控制材料在反复脱嵌钠离子过程中发生结构坍塌程度，能提高钠离子电池层状氧化物正极材料的结构稳定性和循环寿命。
This invention relates to the field of sodium-ion battery electrode material preparation technology, and particularly to a thermoelectric effect NbSe₂ surface-modified O₃-type layered oxide cathode material and its preparation method. The NbSe₂ surface-modified O₃-type layered oxide cathode material uses a sodium - ion battery layered oxide cathode material with the chemical formula NaNiₓFe₂yMn₂z₂ as a substrate, wherein 0.2≤x≤0.4, 0.2≤y≤0.4, and 0.2≤z≤0.4. An NbSe₂ coating layer is constructed on the surface of the substrate, and the mass ratio of NbSe₂ to the sodium - ion battery layered oxide cathode material NaNiₓFe₂yMn₂z₂ is 1: 50–200 . NbSe₂ acts as a protective layer, stably coating the surface of the sodium-ion battery layered oxide cathode material, mitigating side reactions of the cathode material, effectively controlling the degree of structural collapse during repeated sodium ion insertion/extraction, and improving the structural stability and cycle life of the sodium-ion battery layered oxide cathode material.
Description
Technical Field
The invention relates to the technical field of preparation of sodium ion battery electrode materials, in particular to a thermoelectric effect NbSe 2 surface modified O3 type layered oxide positive electrode material and a preparation method thereof.
Background
Currently, efforts are being made worldwide to achieve low-carbon conversion of energy structures, with secondary batteries and energy storage devices being one of the keys to achieve conversion with assistance. Lithium ion batteries are important members of secondary batteries, but they are affected by resource scarcity and safety problems, and research on sodium ion batteries has come back into the public view. The sodium ion battery has good advantages in raw material supply, safety performance and cost. The stability of the positive electrode material directly influences the service life and the safety of the battery. Currently, the types of positive electrode materials include polyanion compounds, prussian blue analogues, layer peroxides, and organic polymers. The layered oxide has high specific capacity and high compaction density, and the production process is similar to ternary lithium ion battery, and is considered as the main direction of research of the current positive electrode material of sodium ion battery.
However, the conventional layered oxide cathode material has the problems of rapid capacity decay and slow sodium ion kinetics in the cycle process, mainly because sodium ions can undergo irreversible phase change in the deintercalation process, such as irreversible phase change of P2-O2 under high potential, and phase change of O3-phase material is more complex, which can lead to the decay of battery energy density and cycle life to some extent. In addition, the kinetic performance of the sodium with larger ionic radius in the repeated deintercalation process is poor, and simultaneously, the decomposition of the material possibly accompanies exothermic reaction, so that the occurrence of surface side reaction is promoted, and the electrochemical performance is deteriorated. These problems limit the marketable applications of sodium ion batteries.
Aiming at the defects of the layered oxide cathode material, the current modification strategies mainly comprise element doping, multiphase symbiosis, surface/interface modification and the like, but no report is made on the surface modification of the sodium ion battery cathode material by using NbSe 2 at present.
Disclosure of Invention
The invention aims to provide a thermoelectric effect NbSe 2 surface modified O3 type layered oxide positive electrode material and a preparation method thereof, aiming at the problems.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The invention provides a thermoelectric effect NbSe 2 surface modified O3 type layered oxide positive electrode material, which takes a sodium ion battery layered oxide positive electrode material with a chemical formula of NaNi xFeyMnzO2 as a matrix, wherein x is more than or equal to 0.2 and less than or equal to 0.4,0.2 and y is more than or equal to 0.4,0.2 and z is more than or equal to 0.4, a NbSe 2 coating layer is constructed on the surface of the matrix, and the mass ratio of NbSe 2 to sodium ion battery layered oxide positive electrode material NaNi xFeyMnzO2 is 1:50-200.
In addition, the invention also provides a preparation method for preparing the thermoelectric effect NbSe 2 surface modified sodium ion battery O3 type layered oxide positive electrode material, which comprises the following steps:
1) Weighing nickel oxide, iron oxide and manganese oxide according to the molar ratio of Ni, fe and Mn elements in the chemical formula of the layered oxide anode material NaNi xFeyMnzO2 of the sodium ion battery;
2) Adding absolute ethyl alcohol into nickel oxide, iron oxide and manganese oxide, and carrying out sanding and mixing treatment;
3) Drying the suspension after sand grinding and mixing;
4) Uniformly mixing the dried mixture with sodium salt, and calcining in air atmosphere to obtain the layered oxide anode material NaNi xFeyMnzO2 of the sodium ion battery;
5) Dissolving a niobium source and a selenium source in ethanol, then adding the sodium ion battery layered oxide anode material NaNi xFeyMnzO2 obtained in the step 4), and evaporating at 80-100 ℃ to form powder;
6) And 5) drying and crushing the powder obtained in the step 5), and calcining under an argon or argon-hydrogen mixed atmosphere to obtain the NbSe 2 surface modified sodium ion battery layered oxide cathode material.
Preferably, in the step 1) of the preparation method, the nickel oxide is one or more of nickel protoxide and nickel sesquioxide, the iron oxide is one or more of ferric oxide and ferroferric oxide, and the manganese salt is one or more of manganese monoxide, manganese dioxide and manganese sesquioxide.
Preferably, in the step 2) of the preparation method, the specific steps of the sand milling and mixing treatment are as follows:
1) Adding nickel oxide, iron oxide, manganese oxide and absolute ethyl alcohol into a material tank of a sand-milling stirring dispersing multipurpose machine, and stirring and dispersing the mixture into suspension, wherein the dosage of the absolute ethyl alcohol is not more than 2/3 of that of the material tank of the sand-milling stirring dispersing multipurpose machine, and the rotating speed of the sand-milling stirring dispersing multipurpose machine is 50-2000 r/min;
2) The material tank of the sand grinding and stirring dispersing multipurpose machine is connected with the feed inlet of the horizontal sand mill through a pipeline, a pumping and conveying suspension liquid of the horizontal sand mill is started to enter a sand grinding cavity, and a main machine of the horizontal sand mill is started to perform sand grinding treatment, wherein the pumping flow of the horizontal sand mill is 50-450 m < 3 >/h, the rotating speed of the main machine of the sand mill is 100-3000r/min, and the duration is 2-10h.
Preferably, in the step 3) of the preparation method, the specific step of drying is that after the sand milling and mixing treatment, the suspension is placed at 80-120 ℃ and dried for 8-12 h.
Preferably, the sodium salt in the step 4) of the preparation method is one or more of sodium hydroxide, sodium carbonate and sodium acetate.
Preferably, the molar ratio of the dried mixture to the sodium salt in step 4) of the preparation method is 1:1.03-1:1.08.
Preferably, the specific steps and conditions of the calcination in the step 4) of the preparation method are that the temperature is firstly increased to 350-500 ℃ at the temperature rising rate of 1-5 ℃ per minute for presintering for 4-6 hours, then the temperature is increased to 800-950 ℃ at the temperature rising rate of 1-5 ℃ per minute for 14-20 hours, and when the temperature is reduced to 600-350 ℃, the temperature is kept for 3-5 hours.
Preferably, the selenium source in the step 5) of the preparation method is one or more of selenium powder and selenium dioxide, and the niobium source is one or more of niobium pentoxide and niobium pentachloride.
Preferably, the drying condition in the step 6) of the preparation method is that the vacuum drying is carried out at 80-120 ℃, and the calcining condition is that the temperature is raised to 300-500 ℃ at the temperature rising rate of 1-5 ℃ per minute, and the heat is preserved for 0.5-6 hours.
In summary, due to the adoption of the technical scheme, the invention has the following beneficial effects:
1. The NbSe 2 coating structure provided by the invention realizes triple function coordination by converting heat energy generated by lattice oxygen precipitation, sodium ion deintercalation thermal effect and side reaction heat release due to oxygen anion redox reaction O 2-→OX- (X < 2) in the material circulation process into electric energy, wherein ① dynamically eliminates heat accumulation, inhibits oxygen precipitation and electrolyte decomposition induced by oxygen vacancies, ② stabilizes a crystal frame structure, reduces interlayer collapse rate caused by repeated deintercalation of sodium ions, ③ forms a physical and chemical barrier, and reduces side reaction between the surface of an anode and electrolyte. Compared with the traditional coating technology, the capacity retention rate of the material is improved to 92.3% after the material is cycled for 200 times at a high voltage of 4.3V by a thermoelectric structure-dual stabilization mechanism.
2. In the thermoelectric effect NbSe 2 surface modified sodium ion battery positive electrode material prepared by the invention, nbSe 2 reacts with residual alkali on the surface of the sodium ion battery layered oxide positive electrode material or is doped in the secondary interior of the material under the high temperature, ar or Ar/H 2 atmosphere to stabilize the structure of the positive electrode material, a thermoelectric effect NbSe 2 coating is formed on the particle surface, the coating is used as a protective layer to stably cover the surface of the sodium ion battery layered oxide positive electrode material in a high voltage state, and simultaneously, the heat in the battery can be relieved, so that oxygen precipitation is slowed down, the material structure is stabilized, and simultaneously, nbSe 2 is used as a protective layer to stably cover the surface of the sodium ion battery layered oxide positive electrode material, so that side reaction of the positive electrode material can be relieved, the occurrence of structural collapse degree of the material in the repeated sodium ion removal process can be effectively controlled, and the structural stability and the cycle life of the sodium ion battery layered oxide positive electrode material can be improved.
3. In the positive electrode material of the thermoelectric effect NbSe 2 surface modified sodium ion battery, nbSe 2 is used as a protective layer to be stably coated on the surface of the positive electrode material of the sodium ion battery, moisture in air is prevented from directly contacting the positive electrode material, side reactions of the positive electrode material are relieved, in addition, nbSe 2 has a thermoelectric effect, the positive electrode material coated by the coating can convert generated heat energy into electric energy in a charge and discharge process, so that the sodium ion conduction rate is improved, meanwhile, structural collapse is caused due to the fact that crystal lattice oxygen is separated out in an exothermic process, the service life of the material is reduced, and NbSe 2 serving as a protective layer to be stably coated on the surface of the positive electrode material of the sodium ion battery can effectively control the structural collapse degree of the material in the repeated sodium ion deintercalation process, and the structural stability and the cycle life of the positive electrode material of the layered oxide of the sodium ion battery are improved.
4. The preparation method provided by the invention combines sand milling and solid-phase sintering, is simple and easy to operate, the anode material used by the invention is composed of manganese element, iron element and the like, and has low cost and environmental friendliness compared with expensive cobalt element, and the NbSe 2 coating with thermoelectric effect generated by the preparation method is used as a protective layer to stably cover the surface of the sodium ion battery layered oxide anode material, so that the side reaction of the anode material can be relieved, the structural collapse degree of the material in the repeated sodium ion removal and intercalation process can be effectively controlled, and the structural stability and the cycle life of the sodium ion battery layered oxide anode material can be improved.
Drawings
FIG. 1 is an XRD pattern of a thermoelectric effect NbSe 2 coating surface modified sodium ion battery layered oxide positive electrode material and a sodium ion battery layered oxide positive electrode material;
FIG. 2 is an SEM image of an unmodified layered oxide positive electrode material of a sodium ion battery;
FIG. 3 is an SEM image of a layered oxide cathode material of a thermoelectric effect NbSe 2 coating surface modified sodium ion battery of the invention;
FIG. 4 is a graph showing initial charge and discharge at a current density of 0.1C for a surface modified layered oxide positive electrode material for sodium ion batteries and an unmodified layered oxide positive electrode material for sodium ion batteries coated with a thermoelectric effect NbSe 2 according to the present invention;
FIG. 5 is a graph showing discharge cycles of a thermoelectric effect NbSe 2 coated surface modified layered sodium-ion battery oxide cathode material and an unmodified layered sodium-ion battery oxide cathode material of the present invention at a current density of 1.0C;
Detailed Description
The invention provides a thermoelectric effect NbSe 2 surface modified O3 type layered oxide positive electrode material, which takes a sodium ion battery layered oxide positive electrode material with a chemical formula of NaNi xFeyMnzO2 as a matrix, wherein x is more than or equal to 0.2 and less than or equal to 0.4,0.2 and y is more than or equal to 0.4,0.2 and z is more than or equal to 0.4, a NbSe 2 coating layer is constructed on the surface of the matrix, and the mass ratio of NbSe 2 to sodium ion battery layered oxide positive electrode material NaNi xFeyMnzO2 is 1:50-200.
The invention will be further illustrated by the following examples, which are given by way of illustration and not limitation, in order to more clearly demonstrate the invention.
Example 1:
the embodiment prepares a thermoelectric effect NbSe 2 surface modified O3 type layered oxide positive electrode material, and the specific preparation method comprises the following steps:
1) 297.8g of nickel oxide, 159.2g of ferric oxide and 283.5g of manganese monoxide are respectively weighed according to the molar ratio of Ni to Fe to Mn=0.4:0.2:0.4 in the chemical formula NaNi 0.4Fe0.2Mn0.4O2 of the layered oxide positive electrode material of the sodium ion battery;
2) The method comprises the steps of weighing nickel protoxide, ferric oxide and manganese monoxide, pouring the nickel protoxide, the ferric oxide and the manganese monoxide into a sand grinding stirring dispersing multipurpose machine material tank filled with 1000mL of absolute ethyl alcohol, wherein the amount of the absolute ethyl alcohol of a solvent is not more than 2/3 of the capacity of the material tank, adjusting the rotating speed of the sand grinding stirring dispersing multipurpose machine to 50 r/min, stirring and dispersing the materials to form suspension, connecting the sand grinding stirring dispersing multipurpose machine material tank with a feeding port of a horizontal sand mill through a pipeline, adjusting the pumping flow of the horizontal sand mill to 250 m < 3 >/h, starting the pumping conveying suspension of the horizontal sand mill to enter a sand grinding cavity, and starting a main machine of the horizontal sand mill to perform sand grinding treatment at the rotating speed of 3000r/min for 6h;
3) Drying the suspension after sand milling and mixing, namely pouring the suspension into a stainless steel container with the thickness of 100cm multiplied by 50cm after sand milling and mixing treatment, and placing the stainless steel container into a blast drying box, wherein the temperature is set to 80 ℃, and the drying time is 12 hours, so as to obtain a dried mixture Ni 0.4Fe0.2Mn0.4 O;
4) 1.3013g of dried mixture Ni 0.4Fe0.2Mn0.4 O and 0.7383g of sodium hydroxide are respectively weighed according to the mol ratio of 1:1.03, uniformly mixed, then heated to 350 ℃ at the heating rate of 1-5 ℃ per minute in air atmosphere, presintered for 5 hours at 350 ℃, then heated to 900 ℃ at the heating rate of 1-5 ℃ per minute, and calcined for 15 hours at 900 ℃, thus obtaining NaNi 0.4Fe0.2Mn0.4O2 g of layered oxide anode material of a sodium ion battery;
5) Dissolving 0.0062g of selenium powder and 0.0054g of niobium pentoxide in 25mL ethanol, adding 2.000g of sodium ion battery layered oxide positive electrode material NaNi 0.4Fe0.2Mn0.4O2（NbSe2 and NaNi 0.4Fe0.2Mn0.4O2 prepared in the step 4) into the mixture, and slowly evaporating the mixture at 80 ℃ to dryness to form powder;
6) And 5) vacuum drying and crushing the powder obtained in the step 5) at 120 ℃, heating to 350 ℃ at a heating rate of 1-5 ℃ per minute in argon atmosphere, and calcining for 1 hour at 350 ℃ to obtain the thermoelectric effect NbSe 2 surface modified sodium ion battery anode material, namely the thermoelectric effect NbSe 2 surface modified O3 layered oxide anode material.
As shown in fig. 1, the surface modification of the sodium-ion battery positive electrode material by the thermoelectric effect NbSe 2 is basically consistent with the XRD pattern of the sodium-ion battery layered oxide positive electrode material before modification, that is, the surface modification of the NbSe 2 coating does not cause the change of the structure of the sodium-ion battery layered oxide positive electrode material.
The SEM images of the thermoelectric effect NbSe 2 surface modified sodium ion battery positive electrode material and the sodium ion battery layered oxide positive electrode material (before coating modification) obtained in this embodiment are shown in fig. 2 and fig. 3, and it can be seen from comparison of fig. 2 and fig. 3 that the NbSe 2 coating layer uniformly coats the surface of the sodium ion battery layered oxide positive electrode material, so that the originally rough surface becomes smoother, thereby reducing residual alkali compounds on the surface of the material and inhibiting the occurrence of interfacial side reaction.
The thermoelectric effect NbSe 2 surface modified sodium ion battery layered oxide positive electrode material and the unmodified sodium ion battery layered oxide positive electrode material prepared in the embodiment are respectively mixed with conductive carbon black super P and a binder PVDF according to the mass ratio of 8:1:1, then N-methyl pyrrolidone is added and uniformly stirred, the obtained slurry is coated on a current collector aluminum foil, the positive electrode plate is prepared by drying at 120 ℃, a metal sodium plate is used as a negative electrode, glass fiber is used as a diaphragm and NaClO 4 is used as an electrolyte, a CR2032 type button experiment battery is assembled in a glove box filled with argon, and the obtained battery is subjected to charge-discharge cycle test under the multiplying power of 1.0C, wherein the test result is shown in figures 4-5.
FIG. 4 is an initial charge-discharge plot of voltage 2.0-4.0V, with a modified specific discharge capacity of 127.99mAh g -1 at 0.1C increased by 5.82mAh g -1 over unmodified 122.17mAh g -1.
As shown in FIG. 5, the initial discharge specific capacity of the surface modified sodium ion battery layered oxide positive electrode material of the thermoelectric effect NbSe 2 prepared by the method is 118.51mAh g -1 at 1C, the discharge specific capacity of the surface modified sodium ion battery layered oxide positive electrode material is 90.14mAh g -1 after 200 cycles, the cycle retention rate is about 76.06%, the initial discharge specific capacity of the battery made of the sodium ion battery layered oxide positive electrode material at 1C is 104.67mAh g -1, the discharge specific capacity of the battery layered oxide positive electrode material after 200 cycles is 53.80mAh g -1, and the cycle retention rate is only 51.40%.
From the results, the surface modified sodium-ion battery layered oxide positive electrode material coated by the thermoelectric effect NbSe 2 has stable structure and good cycle stability.
Example 2:
the embodiment prepares a thermoelectric effect NbSe 2 surface modified O3 type layered oxide positive electrode material, and the specific preparation method comprises the following steps:
1) 297.8g of nickel oxide, 159.2g of ferric oxide and 283.5g of manganese monoxide are respectively weighed according to the molar ratio of Ni to Fe to Mn=0.4:0.2:0.4 in the chemical formula NaNi 0.4Fe0.2Mn0.4O2 of the layered oxide positive electrode material of the sodium ion battery;
2) The method comprises the steps of weighing nickel protoxide, ferric oxide and manganese monoxide, pouring the nickel protoxide, the ferric oxide and the manganese monoxide into a sand grinding stirring dispersing multipurpose machine material tank filled with 1000mL of absolute ethyl alcohol, wherein the amount of the absolute ethyl alcohol of a solvent is not more than 2/3 of the capacity of the material tank, adjusting the rotating speed of the sand grinding stirring dispersing multipurpose machine to 500 r/min, stirring and dispersing the materials to be suspension, connecting the sand grinding stirring dispersing multipurpose machine material tank with a feeding port of a horizontal sand mill through a pipeline, adjusting the pumping flow of the horizontal sand mill to 200 m < 3 >/h, starting the pumping conveying suspension of the horizontal sand mill to enter a sand grinding cavity, and starting a main machine of the horizontal sand mill to perform sand grinding treatment at the rotating speed of 3000r/min for 5h;
3) Drying the suspension after sand milling and mixing, namely pouring the suspension into a stainless steel container with the thickness of 100cm multiplied by 50cm after sand milling and mixing treatment, and placing the stainless steel container into a blast drying box, wherein the temperature is set to 90 ℃, and the drying time is 11 hours, so as to obtain a dried mixture Ni 0.4Fe0.2Mn0.4 O;
4) 1.638g of dried mixture Ni 0.4Fe0.2Mn0.4 O and 0.7524g of sodium hydroxide are respectively weighed according to the mol ratio of 1:1.05, uniformly mixed, then heated to 450 ℃ at the heating rate of 1-5 ℃ per minute in the air atmosphere, presintered for 5 hours at 450 ℃, then heated to 900 ℃ at the heating rate of 1-5 ℃ per minute, calcined for 15 hours at 900 ℃, cooled to 600 ℃ and kept for 3 hours, thus obtaining NaNi 0.4Fe0.2Mn0.4O2 g of sodium ion battery layered oxide anode material 2.0000;
5) Dissolving 0.0177g of selenium dioxide and 0.0106g of niobium pentoxide in 25mL of ethanol, adding 2.0000g of the sodium ion battery layered oxide anode material NaNi 0.4Fe0.2Mn0.4O2（NbSe2 and NaNi 0.4Fe0.2Mn0.4O2 prepared in the step 4) to the mixture in a mass ratio of about 1:100), and slowly evaporating the mixture at 80 ℃ to form powder;
6) And 5) vacuum drying and crushing the powder obtained in the step 5) at 120 ℃, heating to 350 ℃ at a heating rate of 1-5 ℃ per minute in argon-hydrogen atmosphere with the concentration of H 2%, and calcining for 1 hour at 350 ℃ to obtain the thermoelectric effect NbSe 2 surface modified sodium ion battery anode material, namely the thermoelectric effect NbSe 2 surface modified O3 type layered oxide anode material.
The structures of the matrix and the product of this example are identical to those of example 1, and the relevant test patterns and analyses are omitted here.
Example 3:
the embodiment prepares a thermoelectric effect NbSe 2 surface modified O3 type layered oxide positive electrode material, and the specific preparation method comprises the following steps:
1) 297.8g of nickel oxide, 159.2g of iron oxide and 283.5g of manganese monoxide are weighed out according to the molar ratio of Ni to Fe to Mn=0.4:0.2:0.4 in the chemical formula NaNi 0.4Fe0.2Mn0.4O2 of the layered oxide positive electrode material of the sodium ion battery.
2) The method comprises the steps of weighing nickel protoxide, ferric oxide and manganese monoxide, pouring the nickel protoxide, the ferric oxide and the manganese monoxide into a sand grinding stirring dispersing multipurpose machine material tank filled with 1000mL of absolute ethyl alcohol, taking the absolute ethyl alcohol of solvent as much as 2/3 of the capacity of the material tank, adjusting the rotating speed of the sand grinding stirring dispersing multipurpose machine to 1000 r/min, stirring and dispersing the materials to be suspension, connecting the sand grinding stirring dispersing multipurpose machine material tank with a feed inlet of a horizontal sand mill through a pipeline, adjusting the pumping flow of the horizontal sand mill to 300 m < 3 >/h, starting a pumping conveying suspension of the horizontal sand mill to enter a sand grinding cavity, and starting a main machine of the horizontal sand mill to perform sand grinding treatment at the rotating speed of 3000r/min for 4h;
3) Drying the suspension after sand milling and mixing, namely pouring the suspension into a stainless steel container with the thickness of 100cm multiplied by 50cm after sand milling and mixing treatment, and placing the stainless steel container into a blast drying box, wherein the temperature is set to be 100 ℃, and the drying time is 10 hours, so as to obtain a dried mixture Ni 0.4Fe0.2Mn0.4 O;
4) 1.638g of dried mixture Ni 0.4Fe0.2Mn0.4 O and 1.5140g of sodium acetate are respectively weighed according to the mol ratio of 1:1.03, uniformly mixed, heated to 450 ℃ at the heating rate of 1-5 ℃ per minute in the air atmosphere, presintered for 5 hours at 450 ℃, then heated to 950 ℃ at the heating rate of 1-5 ℃ per minute, calcined for 15 hours at 950 ℃, cooled to 500 ℃ and kept for 4 hours, thus obtaining 2.0000g of sodium ion battery layered oxide anode material NaNi 0.4Fe0.2Mn0.4O2;
5) Dissolving 0.0177g of selenium dioxide and 0.0125g of niobium pentoxide in ethanol, adding 2.0000g of sodium ion battery layered oxide anode material NaNi 0.4Fe0.2Mn0.4O2（NbSe2 to NaNi 0.4Fe0.2Mn0.4O2 prepared in the step 4) in a mass ratio of about 1:167), and slowly evaporating to dryness at 80 ℃ to form powder;
6) And 5) vacuum drying and crushing the powder obtained in the step 5) at 120 ℃, heating to 350 ℃ at a heating rate of 1-5 ℃ per minute in an argon atmosphere, calcining for 6 hours at 350 ℃, and obtaining the thermoelectric effect NbSe 2 surface modified sodium ion battery anode material, namely the thermoelectric effect NbSe 2 surface modified O3 type layered oxide anode material.
The structures of the matrix and the product of this example are identical to those of example 1, and the relevant test patterns and analyses are omitted here.
Example 4:
the embodiment prepares a thermoelectric effect NbSe 2 surface modified O3 type layered oxide positive electrode material, and the specific preparation method comprises the following steps:
1) According to the molar ratio of Ni to Fe to Mn=1/3:1/3:1/3 in the chemical formula NaNi 1/3Fe1/3Mn1/3O2 of the layered oxide positive electrode material of the sodium ion battery, 247.3g of nickel sesquioxide, 238.8g of ferric oxide and 259.9g of manganese dioxide are respectively weighed;
2) The method comprises the steps of weighing nickel sesquioxide, ferric oxide and manganese dioxide, pouring the nickel sesquioxide, the ferric oxide and the manganese dioxide into a sand grinding stirring dispersing multipurpose machine material tank filled with 1000mL of absolute ethyl alcohol, wherein the amount of the absolute ethyl alcohol of a solvent is not more than 2/3 of the capacity of the material tank, adjusting the rotating speed of the sand grinding stirring dispersing multipurpose machine to 1500 r/min, stirring and dispersing the materials into suspension, connecting the sand grinding stirring dispersing multipurpose machine material tank with a feeding port of a horizontal sand mill through a pipeline, adjusting the pumping flow of the horizontal sand mill to 50m <3 >/h, starting the pumping conveying suspension of the horizontal sand mill to enter a sand grinding cavity, and starting a main machine of the horizontal sand mill to perform sand grinding treatment at the rotating speed of 3000r/min for 2h;
3) Drying the suspension after sand milling and mixing, namely pouring the suspension into a stainless steel container with the thickness of 100cm multiplied by 50cm after sand milling and mixing treatment, and placing the stainless steel container into a blast drying box, wherein the temperature is set to be 110 ℃, and the drying time is 9 hours, so as to obtain a dried mixture Ni 1/3Fe1/3Mn1/3 O;
4) 1.638g of dried mixture Ni 1/3Fe1/3Mn1/3 O and 0.9971 of sodium carbonate are respectively weighed according to the mol ratio of 1:1.05, uniformly mixed, then heated to 350 ℃ at the heating rate of 1-5 ℃ per minute in air atmosphere, presintered for 4 hours at 350 ℃, then heated to 900 ℃ at the heating rate of 1-5 ℃ per minute, calcined for 14 hours at 900 ℃, cooled to 400 ℃ and kept for 5 hours, and then 2.0000g of sodium-ion battery layered oxide anode material NaNi 1/3Fe1/3Mn1/3O2 can be obtained;
5) 0.0252g of selenium powder and 0.043g of niobium pentachloride are dissolved in 25mL of ethanol, 2.0000g of sodium ion battery layered oxide positive electrode material (the mass ratio of NbSe 2 to NaNi 1/3Fe1/3Mn1/3O2 is about 1:50) prepared in the step 4) is added, and the mixture is slowly evaporated to dryness at 90 ℃ to form powder;
6) And 5) vacuum drying and crushing the powder obtained in the step 5) at 80 ℃, heating to 300 ℃ at a heating rate of 1-5 ℃ per min in an argon-hydrogen mixed atmosphere with the H 2 concentration of 5%, and calcining for 4 hours at 300 ℃ to obtain the thermoelectric effect NbSe 2 surface modified sodium ion battery positive electrode material, namely the thermoelectric effect NbSe 2 surface modified O3 type layered oxide positive electrode material.
The structures of the substrates and products of this example are similar to those of example 1, and the relevant test patterns and analysis are omitted here.
Example 5:
the embodiment prepares a thermoelectric effect NbSe 2 surface modified O3 type layered oxide positive electrode material, and the specific preparation method comprises the following steps:
1) 245.5g of nickel trioxide, 230.3g of ferroferric oxide and 236.03g of manganese trioxide are respectively weighed according to the mole ratio of Ni to Fe to Mn=1/3:1/3:1/3 in the chemical formula NaNi 1/3Fe1/3Mn1/3O2 of the layered oxide positive electrode material of the sodium ion battery.
2) Pouring the weighed nickel sesquioxide, ferroferric oxide and manganese sesquioxide into a sand grinding and stirring dispersing multipurpose machine material tank filled with 1000mL of absolute ethyl alcohol, wherein the amount of the absolute ethyl alcohol of a solvent is not more than 2/3 of the capacity of the material tank, then adjusting the rotation speed of the sand grinding and stirring dispersing multipurpose machine to 2000r/min, stirring and dispersing the materials to be suspension, connecting the sand grinding and stirring dispersing multipurpose machine material tank with a feed inlet of a horizontal sand mill through a pipeline, adjusting the pumping flow of the horizontal sand mill to 450 m < 3 >/h, starting a pumping conveying suspension of the horizontal sand mill to enter a sand grinding cavity, and starting a main machine of the horizontal sand mill to perform sand grinding treatment at the rotation speed of 2000r/min for 10h;
3) Drying the suspension after sand milling and mixing, namely pouring the suspension into a stainless steel container with the thickness of 100cm multiplied by 50cm after sand milling and mixing treatment, and placing the stainless steel container into a blast drying box, wherein the temperature is set to 120 ℃, and the drying time is 8 hours, so as to obtain a dried mixture Ni 1/3Fe1/3Mn1/3 O;
4) 1.638g of dried mixture Ni 1/3Fe1/3Mn1/3 O and 1.0256g of sodium carbonate are respectively weighed according to the mol ratio of 1:1.08, uniformly mixed, heated to 500 ℃ at the heating rate of 1-5 ℃ per minute in air atmosphere, presintered for 6 hours at 500 ℃, then heated to 800 ℃ at the heating rate of 1-5 ℃ per minute, calcined for 20 hours at 800 ℃, cooled to 350 ℃ and kept for 5 hours, and then 2.0000g of sodium-ion battery layered oxide anode material NaNi 1/3Fe1/3Mn1/3O2 can be obtained;
5) Dissolving 0.0250g of selenium dioxide and 0.0305g of niobium pentachloride in ethanol, adding 2.0000g of sodium ion battery layered oxide anode material NaNi 1/3Fe1/3Mn1/3O2（NbSe2 to NaNi 1/3Fe1/3Mn1/3O2 prepared in the step 4) to the mixture, and slowly evaporating the mixture at 100 ℃ to dryness to form powder;
6) And 5) vacuum drying and crushing the powder obtained in the step 5) at 100 ℃, heating to 500 ℃ at a heating rate of 1-5 ℃ per minute in argon atmosphere, and calcining for 0.5 hour at 500 ℃ to obtain the thermoelectric effect NbSe 2 surface modified sodium ion battery anode material, namely the thermoelectric effect NbSe 2 surface modified O3 layered oxide anode material.
The structures of the substrates and products of this example are similar to those of example 1, and the relevant test patterns and analysis are omitted here.
The foregoing description is directed to the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the invention, and all equivalent changes or modifications made under the technical spirit of the present invention should be construed to fall within the scope of the present invention.
Claims (10)
1. The surface modified O3 type layered oxide cathode material of the NbSe 2 with the thermoelectric effect is characterized in that the surface modified O3 type layered oxide cathode material of the NbSe 2 takes a sodium ion battery layered oxide cathode material with a chemical formula of NaNi xFeyMnzO2 as a matrix, wherein x is more than or equal to 0.2 and less than or equal to 0.4,0.2, y is more than or equal to 0.4,0.2 and less than or equal to z is less than or equal to 0.4, a NbSe 2 coating layer is constructed on the surface of the matrix, and the mass ratio of the NbSe 2 to the sodium ion battery layered oxide cathode material NaNi xFeyMnzO2 is 1:50-200.
2. A method for preparing the thermoelectric effect NbSe 2 surface modified sodium ion battery O3 type layered oxide positive electrode material according to claim 1, which is characterized by comprising the following steps:
1) Weighing nickel oxide, iron oxide and manganese oxide according to the molar ratio of Ni to Fe to Mn in the chemical formula NaNi xFeyMnzO2 of the layered oxide positive electrode material of the sodium ion battery as x to y to z;
2) Adding absolute ethyl alcohol into nickel oxide, iron oxide and manganese oxide, and carrying out sanding and mixing treatment;
3) Drying the suspension after sand grinding and mixing;
4) Uniformly mixing the dried mixture with sodium salt, and calcining in air atmosphere to obtain the layered oxide anode material NaNi xFeyMnzO2 of the sodium ion battery;
5) Dissolving a niobium source and a selenium source in ethanol, adding the sodium ion battery layered oxide anode material NaNi xFeyMnzO2 obtained in the step 4), and evaporating at 80-100 ℃ to obtain powder;
6) And 5) drying and crushing the powder obtained in the step 5), and calcining under an argon or argon-hydrogen mixed atmosphere to obtain the NbSe 2 surface modified sodium ion battery layered oxide cathode material.
3. The preparation method of the composite material according to claim 2, wherein in the step 1), the nickel oxide is one or more of nickel oxide and nickel sesquioxide, the iron oxide is one or more of iron oxide and ferroferric oxide, and the manganese oxide is one or more of manganese monoxide, manganese dioxide and manganese sesquioxide.
4. The method according to claim 2, wherein in step 2), the specific steps of the sand-milling mixing process are as follows:
1) Adding nickel oxide, iron oxide, manganese oxide and absolute ethyl alcohol into a material tank of a sand-grinding stirring dispersing multipurpose machine, and stirring and dispersing the mixture into suspension, wherein the rotating speed of the sand-grinding stirring dispersing multipurpose machine is 50-2000 r/min;
2) The material tank of the sand grinding and stirring dispersing multipurpose machine is connected with the feed inlet of the horizontal sand mill through a pipeline, a pumping and conveying suspension liquid of the horizontal sand mill is started to enter a sand grinding cavity, and a main machine of the horizontal sand mill is started to perform sand grinding treatment, wherein the pumping flow of the horizontal sand mill is 50-450 m < 3 >/h, the rotating speed of the main machine of the sand mill is 100-3000r/min, and the duration is 2-10h.
5. The method according to claim 2, wherein in step 3), the specific step of drying is to dry the suspension for 8 to 12 hours at 80 to 120 ℃ after the sand-milling mixing treatment.
6. The preparation method according to claim 2, wherein the sodium salt in the step 4) is one or more of sodium hydroxide, sodium carbonate and sodium acetate.
7. The method according to claim 2, wherein the molar ratio of the dried mixture to sodium salt in step 4) is 1:1.03-1:1.08.
8. The preparation method according to claim 2, wherein the specific steps and conditions of the calcination in the step 4) are that the temperature is raised to 350-500 ℃ at a temperature raising rate of 1-5 ℃ per min, presintering is carried out for 4-6 hours, and then the temperature is raised to 800-950 ℃ at a temperature raising rate of 1-5 ℃ per min, and calcination is carried out for 14-20 hours.
9. The method of claim 2, wherein the selenium source in step 5) is one or more of selenium powder and selenium dioxide, and the niobium source is one or more of niobium pentoxide and niobium pentachloride.
10. The method according to claim 2, wherein the drying condition in the step 6) is vacuum drying at 80-120 ℃, and the calcining condition is heating to 300-500 ℃ at a heating rate of 1-5 ℃ per min, and preserving heat for 0.5-6 hours.
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