CN115692653A - Sodium ion battery positive electrode material and preparation method thereof - Google Patents
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Abstract
The invention provides a positive electrode material of a sodium-ion battery and a preparation method thereof. In the invention, the coating layer is used as a protection unit and does not participate in the redox reaction in the charging and discharging process, so that the volume change stress of the whole material in the circulating process can be reduced, and the circulating stability and the capacity retention rate are improved; meanwhile, in the high-temperature sintering process, metal ions in the coating layer further diffuse and permeate into the positive electrode material to realize doping to form a doping layer, so that the stability and the structural stability of the crystal in the circulating process can be improved, and the capacity retention rate of the positive electrode material in the circulating process can be improved, so that the positive electrode material of the sodium-ion battery has the advantages of high capacity, high circulating stability and air stability.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a sodium ion battery anode material and a preparation method thereof.
Background
The rapid development of portable electronic devices, electric vehicles, and renewable energy sources requires efficient and inexpensive energy storage technologies. Although lithium ion batteries have gained a large market share in these areas, the cost is high, safety issues are severe, and the sustainability of raw materials still needs to be addressed. Recently, sodium ion batteries are considered as one of the effective complement solutions in the application scenario of lithium ion batteries, especially in the fields of large-scale energy storage and low-speed electric vehicle application. Compared with lithium ions, sodium ion resources are more abundant and uniform in global distribution, and most importantly, positive electrode materials and current collectors of a sodium ion battery system are cheaper theoretically.
The search for suitable positive electrode materials is a key to the development of sodium ion batteries. Researchers have reported various types of potential cathode materials, among which the most commonly studied sodium-ion battery cathode materials include polyanionic compounds, layered metal oxides, prussian blue analogs. The layered metal oxide has simple synthesis process and high theoretical capacity, and is considered to be the sodium-ion battery positive electrode material expected to realize commercial application most quickly.
However, the sodium-based layered oxide generally has a larger interlayer distance than lithium, accelerates the reaction of intercalated sodium with air, and has a stronger reactivity when exposed to air. This ultimately results in higher manufacturing, storage, and pole piece manufacturing costs for the sodium-ion battery, which greatly hinders practical application of the sodium-ion battery. Meanwhile, the oxidation of the layered metal has multiphase phase change in the circulation process to cause structural change, and the poor circulation stability is shown. Therefore, in order to promote the practical application of the sodium ion battery, the defects of poor air stability and poor circulation stability of the sodium ion battery are overcome by using a low-cost process mode, and the method has important significance for the application and popularization of the sodium ion battery.
Chinese patent 107369826A discloses a doping and coating double-modified lithium/sodium layered metal oxide positive electrode material and a one-step synthesis method thereof. The surface of a precursor is coated with lanthanide series or actinide series ionic compounds by a sol method or a solid phase ball milling method, and metal or nonmetal doping is carried out at the same time, so that the electrochemical performance of the anode material is obviously improved by utilizing the double modification. However, the coating layer is made of rare earth elements such as lanthanide series and the like, is expensive and not easy to obtain, and is not in accordance with the original purpose of development and design of a sodium ion battery as a low-cost energy storage device; meanwhile, the sol method or the solid phase ball milling method has the problems of low yield, poor process stability and the like in large-scale production.
Chinese patent CN113937286A discloses a coating modified sodium ion battery anode material and a preparation method thereof, wherein firstly, an ion-doped anode material is synthesized, and then a manganese-rich shell layer is coated on the surface of the anode material. However, the method needs a two-step sintering process, the first step sintering is used for preparing the layered metal oxide, the second step sintering is used for preparing the layered metal oxide with a coating structure, the two-step sintering process is high in energy consumption, the coating layer also participates in the redox reaction in the charging and discharging process, the change of a crystal phase exists, the circulation stability of the material is poor, and the capacity retention rate is only about 85% after 100 cycles.
Therefore, there is a need to develop a sodium ion battery cathode material with cheap and easily available structural composition and air stability and cycling stability, and to design a preparation method which is simple in process and can be applied in a large scale for preparing the sodium ion battery cathode material.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a positive electrode material for a sodium-ion battery, which has advantages of high capacity, high cycle stability and air stability.
In order to achieve the above object, a first aspect of the present invention provides a sodium-ion battery positive electrode material, including a core body and a coating layer coating the core body, wherein a doping layer is provided between the core body and the coating layer, the core body is a layered metal oxide, the coating layer is a metal oxide, and metal ions in the coating layer metal oxide penetrate into the core body to be doped to form the doping layer.
According to the sodium ion battery positive electrode material, the coating layer is formed on the surface of the core body, the doping layer is arranged between the core body and the coating layer, the surface of the core body is coated, so that good air stability can be achieved, particularly, metal ions in the coating layer can diffuse and permeate into the layered metal oxide core body to be doped in the sintering process, and the metal ions in the metal oxide of the coating layer permeate to form the doping layer. On one hand, the doping element improves the crystal stability of the anode material in the circulating process, and on the other hand, the coating layer and the core body have no obvious layer boundary, so that the coating layer and the core body are combined more tightly, and the structural stability is improved. Therefore, the positive electrode material of the sodium-ion battery has the advantages of high capacity, high cycle stability and air stability, and has excellent electrochemical performance.
In some embodiments, the layered metal oxide has the formula Na x M1 a M2 b M3 c O 2 Wherein M1, M2 and M3 are transition metal elements, x is more than or equal to 0.2 and less than or equal to 1, a + b + c =1, a is more than or equal to 0 and less than or equal to 1,0 and less than or equal to b is more than or equal to 1,0 and less than or equal to c is less than or equal to 1.
In some embodiments, M1, M2, M3 each independently comprise at least one of Ni, fe, mn, co, cu, cr, V.
In some embodiments, na x M1 a M2 b M3 c O 2 Is O3 phase, P2 phase or O3/P2 mixed phase layered metal oxide.
In some embodiments, the metal oxide has the formula M y O z Wherein M comprises at least one of Ge, rb, cd, zn, zr, mg, al, nb, ti, sn, ca, ru, mo, sb, sr and Ag, and y is more than 0 and less than or equal to 3,0 and z is more than or equal to 5.
In some embodiments, the doping element of the doping layer is said metal oxide M y O z The metal M in (1).
In some embodiments, the cladding layer has a thickness of 100nm to 1 μm.
In some embodiments, the doped layer has a metal doping depth of 50 to 200nm.
In some embodiments, the coating material comprises 0.1 to 7wt% of the total mass of the core body, coating layer, and doped layer.
The invention also aims to provide a preparation method of the sodium-ion battery anode material, which can simultaneously realize two modification effects of coating and doping by a one-step sintering process, simplify the production process, reduce the production cost and facilitate expanded production.
In order to achieve the above object, a second aspect of the present invention provides a method for preparing a positive electrode material for a sodium-ion battery, comprising the steps of:
(a) Mixing a sodium source, a metal source and a first solvent to prepare slurry, and preparing precursor powder A after sand grinding and spray granulation of the slurry;
(b) Adding the precursor powder A into a second solvent, heating and stirring, adding a solution containing metal M, and removing the second solvent to obtain precursor powder B;
(c) And sintering the precursor powder B under the atmosphere with a certain oxygen content, and then cooling and grinding to obtain the metal M-doped sodium-ion battery positive electrode material coated by the oxide of the metal M.
In the preparation method of the positive electrode material of the sodium-ion battery, slurry is subjected to sanding treatment and spray granulation to prepare precursor powder A, then a solution containing metal M is added, the second solvent is removed to obtain precursor powder B, and finally the positive electrode material of the sodium-ion battery is prepared by adopting a sintering process; the spray granulation can make the particles into spheres, the spherical particle precursor ensures that the particles directly have certain gaps, the gas emission and the oxygen contact in the sintering process are facilitated, and the forward proceeding of the reaction is ensured. If the conventional evaporation drying is adopted, the crystallization of sodium carbonate is easy to separate out, and the uniform appearance and granularity of the dried material are difficult to ensure. Therefore, the invention realizes two modification effects of coating and doping by a one-step method, has stable and reliable process and good product uniformity and is beneficial to large-scale production.
In some embodiments, the metal source comprises at least one of an M1 metal source, an M2 metal source, and an M3 metal source, the M1 metal source, the M2 metal source, and the M3 metal source all being from a transition metal element.
In some embodiments, the M1 metal source, the M2 metal source, and the M3 metal source each independently comprise at least one of nickel oxide, iron oxide, manganese oxide, cobalt oxide, copper oxide, chromium oxide, and vanadium oxide.
In some embodiments, the sodium source comprises at least one of sodium carbonate, sodium bicarbonate, sodium nitrate, sodium hydroxide.
In some embodiments, the first solvent is selected from at least one of deionized water, ethanol, methanol, isopropanol, triethylene glycol, polyethylene glycol, acetone, N-methylpyrrolidone.
In some embodiments, the particle size of the slurry after sanding is controlled to be 50nm D50 less than or equal to 1 μm and 200nm D90 less than or equal to 2 μm.
In some embodiments, the precursor powder A has a particle size of 1 μm D50 20 μm.
In some embodiments, in step (b), the second solvent is selected from at least one of de-ethanol, methanol, isopropanol, triethylene glycol, polyethylene glycol, acetone, N-methylpyrrolidone.
In some embodiments, the temperature of the heating and stirring in step (b) is 30 to 100 ℃.
In some embodiments, in step (b), the heating and stirring time is 8 to 24 hours.
In some embodiments, in step (c), the temperature of the sintering is 600 to 1000 ℃.
In some embodiments, in step (c), the sintering time is 10 to 25 hours.
In some embodiments, in step (c), the oxygen-containing atmosphere is a gas containing 20 to 80% oxygen.
In some embodiments, in step (c), the flow rate of the oxygen content atmosphere is 1L/min to 20L/min.
Drawings
Fig. 1 is a schematic diagram illustrating the effect of coating doping double modification of the positive electrode material of the sodium-ion battery.
Fig. 2 is an SEM image of the positive electrode material of the sodium-ion battery of example 1 of the present invention.
Fig. 3 is an SEM image of the positive electrode material of the sodium-ion battery of comparative example 1.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and improvements without departing from the principle of the embodiments of the present invention, and such modifications and improvements are considered to be within the scope of the embodiments of the present invention.
Referring to fig. 1, a positive electrode material for a sodium ion battery according to an embodiment includes a core body and a coating layer covering the core body, a doping layer is disposed between the core body and the coating layer, the core body is a layered metal oxide, the coating layer is a metal oxide, and metal ions in the coating layer penetrate into the core body to be doped to form the doping layer.
It can be understood that, in the sodium ion battery positive electrode material of the embodiment, the coating layer is formed on the surface of the core body, the doping layer is arranged between the coating layer and the core body, and the surface of the core body is coated by the coating layer, so that the positive electrode material has better air stability. On one hand, the metal doping element can improve the crystal stability of the anode material in the circulating process, and on the other hand, the coating layer and the core body have no obvious layer boundary, so that the coating layer and the core body are combined more tightly, and the structural stability is improved. Therefore, the positive electrode material of the sodium-ion battery has the advantages of high capacity, high cycle stability and air stability, and has excellent electrochemical performance.
In some embodiments, the layered metal oxide has the formula Na x M1 a M2 b M3 c O 2 Wherein M1, M2 and M3 are transition metal elements, x is more than or equal to 0.2 and less than or equal to 1, a + b + c =1, a is more than or equal to 0 and less than or equal to 1,0 and less than or equal to b is more than or equal to 1,0 and less than or equal to c is less than or equal to 1. For example, x may be 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.85, 0.9, or 1.0, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned ranges are also applicable, and x in the present embodiment has a value of 1. For example, a may be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.85, 0.9, or 1.0, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned numerical ranges are also applicable, and a may be 1/3, 1/6, or the like in the present embodiment. For example, the value of b may be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.85, 0.9, 1.0, but is not limited to the enumerated values, and other unrecited values within the above numerical ranges are also applicable, and the value of b in the present embodiment is 1/3. For example, c may be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.85, 0.9, or 1.0, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned numerical ranges are also applicable, and c may be 1/3, 1/2, or the like in the present embodiment. In certain embodiments, the layered metal oxide contains only one transition metal element M1, a =1, b = c =0, i.e. the layered metal oxide has the formula Na x M1O 2 (ii) a In some examples, the layered metal oxide contains only two transition metal elements M1 and M2, a + b =1, c =0, i.e. the layered metal oxide has the formula Na x M1 a M2 b O 2 If a =1/2, b =1/2, the structure of the layered metal oxide is Na x M1 1/2 M2 1/2 O 2 But is not limited thereto. In still another example, the layered metal oxide contains three transition metal elements M1, M2, and M3, a =0.5, b =0.3, c =0.2, i.e., the layered metal oxide has a structure of Na x M1 0.5 M2 0.3 M3 0.2 O 2 But is not limited thereto.
In some embodiments, the transition metal element includes at least one of Ni, fe, mn, co, cu, cr, V, but not limited toNot limited thereto. The transition metal element has empty d and f orbitals, is convenient for accepting electrons, indirectly facilitates electron transfer, and facilitates the conversion between electric energy and chemical energy to realize the storage and the release of energy. It is understood that M1, M2, M3 each independently comprise at least one of Ni, fe, mn, co, cu, cr, V. Illustratively, M1 comprises at least one of Ni, fe, mn, co, cu, cr, V; m2 comprises at least one of Ni, fe, mn, co, cu, cr and V, and M3 comprises at least one of Ni, fe, mn, co, cu, cr and V. As an example, the layered metal oxide may have the formula Na x Ni a Fe b Mn c O 2 、Na x Cu a Fe b Mn c O 2 、Na x Cu a Co b Cr c O 2 、Na x Ni a V b Mn c O 2 、Na x Ni a Fe b O 2 、Na x Cu a Fe b O 2 、Na x Cu a O 2 、Na x Ni a O 2 But is not limited thereto.
In some embodiments, na x M1 a M2 b M3 c O 2 Is an O3 phase, a P2 phase or an O3/P2 mixed phase layered metal oxide, illustratively, na x M1 a M2 b M3 c O 2 The O3 phase is a layered transition metal oxide with high specific capacity.
In some embodiments, the metal oxide has the formula M y O z Wherein M comprises at least one of Ge, rb, cd, zn, zr, mg, al, nb, ti, sn, ca, ru, mo, sb, sr and Ag, and y is more than 0 and less than or equal to 3,0 and z is more than or equal to 5. For example, y may be 0.1, 0.5, 1, 1.5, 2, 2.5, or 3, but is not limited to the recited values, and other values not recited in the above numerical ranges are also applicable, and y in the present embodiment is 1, 2, or the like; by way of example, z may take the values 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, but is not limited to the values listed and other values not listed within the numerical ranges given above are likewise possibleIn this embodiment, y is 1, 2, 3, 5, etc. Specifically, the metal oxide may be GeO 2 、Rb 2 O、CdO、ZnO、ZrO 2 、MgO、Al 2 O 3 、Nb 2 O 5 、TiO 2 、SnO 2 、CaO、RuO 2 、MoO 2 、Sb 2 O 3 SrO, agO, and the like, but not limited thereto.
In some embodiments, the doping element of the doped layer is a metal oxide M y O z The metal M in (1). As an example, the doping element M comprises at least one of Ge, rb, cd, zn, zr, mg, al, nb, ti, sn, ca, ru, mo, sb, sr, ag. It is to be understood that the metal oxide M of the coating layer is formed during sintering y O z In which M is further converted to Na x M1 a M2 b M3 c O 2 The doping is realized to positive pole material internal diffusion infiltration and is formed the doping layer to the realization makes coating metal and doping layer metal be the same metal, makes coating and nuclear body do not have obvious layer limit, and the combination between the two is inseparabler, promotes structural stability.
In some embodiments, the coating layer has a thickness of 100nm to 1 μm, and the coating layer may have a thickness of 100nm, 140nm, 180nm, 220nm, 250nm, 280nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm, 800nm, 850nm, 950nm, 1 μm, and the like, as examples, but is not limited to the enumerated values, and other values not enumerated within the above numerical ranges may be equally applicable.
In some embodiments, the doping layer metal doping depth is 50 to 200nm, and as an example, the doping layer metal doping depth may be 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 120nm, 140nm, 160nm, 180nm, 200nm, and the like, but is not limited to the recited values, and other values within the above ranges are also applicable.
In some embodiments, the coating layer material comprises 0.1 to 7wt% of the positive electrode material based on 100% of the total mass of the positive electrode material, i.e., the coating layer comprises 0.1 to 7wt% of the total mass of the core body, the coating layer, and the doping layer. By way of example, the mass percent of the cladding material relative to the total mass of the core body, cladding layer, and doped layer can be 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, 5.5wt%, 6wt%, 6.5wt%, or 7wt%, and so forth, but is not limited to the recited values, and other values not recited within the above-recited ranges of values are equally applicable. It can be understood that the content of the coating layer is too low, the coating is difficult to be uniform, and a good coating effect cannot be achieved; too high a coating level results in a relatively low active material level, which affects energy density.
The preparation method of the sodium-ion battery positive electrode material comprises the following steps:
(a) Mixing a sodium source, a metal source and a first solvent to prepare slurry, and preparing precursor powder A after sanding and spray granulation of the slurry;
(b) Adding the precursor powder A into a second solvent, heating and stirring, adding a solution containing metal M, and removing the second solvent to obtain precursor powder B;
(c) And sintering the precursor powder B in the atmosphere with certain oxygen content, and then cooling and grinding to obtain the metal M-doped sodium-ion battery anode material coated by the oxide of the metal M.
According to the preparation method of the sodium-ion battery cathode material, two modification effects of coating and doping can be simultaneously realized through a one-step sintering process, so that the sodium-ion battery cathode material with high capacity, high cycle stability and air stability is obtained, the production process is simple, the production cost is reduced, and the expanded production is easy.
In some embodiments, the sodium source comprises at least one of sodium carbonate, sodium bicarbonate, sodium nitrate, sodium hydroxide. For example, the sodium source may be selected from sodium carbonate, sodium bicarbonate, sodium nitrate, or sodium hydroxide, or may be a combination of sodium carbonate and sodium bicarbonate, a combination of sodium carbonate and sodium nitrate, a combination of sodium carbonate and sodium hydroxide, a combination of sodium bicarbonate and sodium nitrate, a combination of sodium bicarbonate and sodium hydroxide, a combination of sodium nitrate and sodium hydroxide, or the like, but is not limited thereto.
In some embodiments, the metal source comprises at least one of an M1 metal source, an M2 metal source, and an M3 metal source, wherein the M1 metal source, the M2 metal source, and the M3 metal source are from a transition metal element. In certain embodiments, the metal source contains only one transition metal element, M1; in some embodiments, the metal source contains only two transition metal elements, M1 and M2; in still other embodiments, the metal source contains three transition metal elements, M1, M2, and M3, simultaneously.
In some embodiments, the transition metal element comprises at least one of Ni, fe, mn, co, cu, cr, V. For example, the M1 metal source, the M2 metal source, and the M3 metal source are oxides of transition metal elements M1, M2, and M3, respectively, and it is understood that the M1 metal source, the M2 metal source, and the M3 metal source each independently include at least one of nickel oxide, iron oxide, manganese oxide, cobalt oxide, copper oxide, chromium oxide, and vanadium oxide, but are not limited thereto. Illustratively, the M1 metal source comprises at least one of nickel oxide, iron oxide, manganese oxide, cobalt oxide, copper oxide, chromium oxide, vanadium oxide; the M2 metal source comprises at least one of nickel oxide, iron oxide, manganese oxide, cobalt oxide, copper oxide, chromium oxide and vanadium oxide; the M3 metal source comprises at least one of nickel oxide, iron oxide, manganese oxide, cobalt oxide, copper oxide, chromium oxide and vanadium oxide. By way of example, the M1 metal source, the M2 metal source, and the M3 metal source are respectively selected from nickel oxide, iron oxide, and manganese oxide, and for example, the M1 metal source, the M2 metal source, and the M3 metal source are respectively selected from copper oxide, iron oxide, and manganese oxide, but not limited thereto.
In some embodiments, the sodium source: the weight ratio of the metal source is 0.5 to 1, and illustratively, the sodium source: the weight ratio of the metal source may be, but is not limited to, 0.5, 0.6, 0.7, 0.8, 0.9, 1, and is not limited to the recited values, and other values not recited in the above numerical ranges are also applicable.
In some embodiments, the first solvent is at least one selected from the group consisting of deionized water, ethanol, methanol, isopropanol, triethylene glycol, polyethylene glycol, acetone, N-methylpyrrolidone, N-N dimethylformamide, acetone, acetonitrile, and diethyl ether, and a suitable solvent may be selected according to the selected sodium source and metal source.
In some embodiments, the precursor powder a is prepared by spray granulation of a slurry of the sodium source, the metal source, and the first solvent after mixing, i.e., not only granulation is achieved but the first solvent can be removed during the spray granulation. By way of example, but not limitation, spray granulation may be achieved by a spray dryer.
In some embodiments, the sand milling is performed before the spray granulation, that is, a suitable slurry particle size is obtained by a sand milling process, which may be implemented by a sand mill, by way of example, but not limited thereto. Furthermore, the granularity of the slurry after sanding is controlled to be more than or equal to 50nm and less than or equal to D50 and less than or equal to 1 mu m. It is understood that D50 refers to the particle size corresponding to a cumulative percent particle size distribution of a sample up to 50%. Furthermore, the granularity of the slurry after sanding is controlled to be not less than 200nm and not more than D90 and not more than 2 mu m. It is understood that D90 refers to the particle size corresponding to 90% of the cumulative percent particle size distribution for a sample. By way of example, D50 can take the value 50nm, 80nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm or 1 μm, but is not limited to the recited values, and other values not recited within the above numerical ranges are equally applicable. For example, D90 may be 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, 1 μm, 1.2 μm, 1.4 μm, 1.6 μm, 1.8 μm,2 μm, etc., but is not limited to the values listed, and other values not listed in the above numerical ranges are also applicable. In some embodiments, the particle size of the slurry after sanding is controlled to be 200nm or more and D50 or less and 800nm or less.
In some embodiments, the sanding time is 1 to 5 hours, and as an example, the sanding time can be 1 hour, 2 hours, 3 hours, 4 hours, or 5 hours, but is not limited to the recited values, and other values not recited within the above numerical ranges are equally applicable.
In some embodiments, the precursor powder A has a particle size of 1 μm.ltoreq.D 50.ltoreq.20 μm, and may have a particle size of 1 μm,2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm,20 μm, and the like, for example, but not limited to the enumerated values, and other unrecited values within the above numerical ranges may be equally applicable.
In some embodiments, the second solvent is selected from at least one of de-ethanol, methanol, isopropanol, triethylene glycol, polyethylene glycol, acetone, N-methylpyrrolidone, N-N dimethylformamide, acetone, acetonitrile and diethyl ether. Further, ethanol is preferably used as the second solvent.
In some embodiments, the temperature of the heating and stirring is 30 to 100 ℃, and the temperature of the heating and stirring may be, for example, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃,70 ℃, 75 ℃,80 ℃, 85 ℃,90 ℃, 95 ℃,100 ℃ or the like, but is not limited to the recited values, and other values not recited in the above numerical ranges are also applicable.
In some embodiments, the time for heating and stirring is 8 to 24 hours, and the time for heating and stirring can be 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, and the like, by way of example, but is not limited to the recited values, and other values not recited in the above numerical ranges are also applicable.
In some embodiments, the sintering temperature is 600 to 1000 ℃, and the sintering temperature can be, for example, 600 ℃,700 ℃,800 ℃,900 ℃, or 1000 ℃, etc., but is not limited to the recited values, and other values not recited in the above numerical ranges are also applicable. It can be understood that the sintering temperature is too low, the raw materials are difficult to realize sufficient fusion and reaction, the synthesized product deviates from the design value, the crystallinity is poor, and the electrochemical performance is poor; if the sintering temperature is too high, the oxygen loss of the product is easy to cause, the energy consumption is large, the structure and the stability of the product are influenced, and the processing economy is poor.
In some embodiments, the sintering time is 10 to 25 hours, and the sintering time can be, for example, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, or 25 hours, etc., but is not limited to the recited values, and other values within the above ranges are also applicable.
In some embodiments, the oxygen-containing atmosphere is a gas containing 20 to 80% oxygen, and the oxygen content is, for example, 20%, 30%, 40%, 50%, 60%, 70%, or 80%, but not limited to the recited values, and other values within the above-mentioned ranges are also applicable.
In some embodiments, the flow rate of the oxygen-containing atmosphere is 1L/min to 20L/min, and as an example, the flow rate of the oxygen-containing atmosphere can be 1L/min, 2L/min, 3L/min, 4L/min, 5L/min, 6L/min, 7L/min, 8L/min, 9L/min, 10L/min, 11L/min, 12L/min, 13L/min, 14L/min, 15L/min, 16L/min, 17L/min, 18L/min, 19L/min, or 20L/min, and so forth, but is not limited to the recited values, and other non-recited values within the above numerical ranges are equally applicable.
The invention consists of an inert oxide M y O z The shell is coated with Na x M1 a M2 b M3 c O 2 The surface of the inner core (nucleus body) is effectively isolated from Na on one hand x M1 a M2 b M3 c O 2 The coating layer is used as a protection unit and does not participate in the redox reaction in the charging and discharging processes, so that the volume change stress of the whole material in the circulating process can be reduced, and the circulating stability and the capacity retention rate are improved; at the same time, in the process of high-temperature sintering, the coating layer M y O z The metal ion M in (A) is further converted to Na x M1 a M2 b M3 c O 2 The doping is realized by the internal diffusion and penetration of the anode material; namely, the coating doping double modification is realized simultaneously by a one-step sintering method, and on one hand, the Na is doped x M1 a M2 b M3 c O 2 M in (1) can relieve Na in the charge-discharge process x M1 a M2 b M3 c The structure of the O crystal is changed, the stability of the crystal in the circulating process is improved, and on the other hand, the doping mode is adoptedThe coating layer and the core body are not provided with obvious layer boundaries, the combination between the coating layer and the core body is tighter, the structural stability is improved, and the capacity retention rate of the anode material in the circulation process is further improved. The preparation method of the sodium-ion battery anode material adopts a one-step sintering method, does not relate to a complex secondary sintering process, simplifies the process flow, has relatively cheap and easily obtained coated doping elements, reduces the production cost, and is suitable for large-scale production and application and popularization.
To better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples. It should be noted that the following implementation methods are further illustrative of the present invention and should not be construed as limiting the present invention.
Example 1
The positive electrode material of the sodium-ion battery comprises a core body and a coating layer coating the core body, wherein a doping layer is arranged between the core body and the coating layer, and the core body is NaNi 1/3 Fe 1/3 Mn 1/3 O 2 The coating layer is ZrO 2 The doped layer being Zr, called ZrO 2 Coated Zr-doped NaNi 1/3 Fe 1/3 Mn 1/3 O 2 。
The preparation method of the positive electrode material of the sodium-ion battery comprises the following steps:
(1) Stirring and dispersing 74.7g of nickel oxide, 79.8g of iron oxide, 86.9 g of manganese oxide and 158.9g of sodium carbonate in 3000mL of deionized water to prepare slurry;
(2) Pumping the slurry into a sand mill, and performing sand milling treatment for 1h to control the granularity of the slurry to be about D50=500nm and D90=1.2 μm so as to obtain precursor slurry;
(3) Conveying the precursor slurry into a drying tower in a centrifugal spray dryer through a peristaltic pump, and instantly evaporating the solvent to obtain precursor powder A, wherein the granularity D50=10 μm of the precursor powder A;
(4) Taking 100g of precursor powder A, stirring and dispersing in 100ml of ethanol, then adding 30ml of n-butyl alcohol zirconium solution, and continuing stirring for about 20 hours under the condition of 60 ℃ water bath until the solvent is completely evaporated to obtain precursor powder B;
(5) Placing the precursor powder B in a corundum sagger, placing the sagger in a box-type furnace, sintering for 25h at 900 ℃ in the air atmosphere, naturally cooling, crushing and screening the obtained product to obtain ZrO 2 Coated Zr-doped NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Example 2
The positive electrode material of the sodium-ion battery comprises a core body and a coating layer coating the core body, wherein a doping layer is arranged between the core body and the coating layer, and the core body is NaNi 1/3 Fe 1/3 Mn 1/3 O 2 The coating layer is Al 2 O 3 The doped layer being Al, called Al 2 O 3 Coated Al doped NaNi 1/3 Fe 1/3 Mn 1/3 O 2 。
The preparation method of the positive electrode material of the sodium-ion battery comprises the following steps:
(1) Stirring and dispersing 74.7g of nickel oxide, 79.8g of iron oxide, 86.9 g of manganese oxide and 158.9g of sodium carbonate in 3000mL of deionized water to prepare slurry;
(2) Pumping the slurry into a sand mill, and controlling the granularity of the slurry to be about D50=400nm through 1h of sand milling treatment; d90=1.0um or so, and obtaining precursor slurry;
(3) Conveying the precursor slurry into a drying tower in a centrifugal spray dryer through a peristaltic pump, and instantaneously evaporating a solvent to obtain precursor powder A, wherein the granularity D50=8 μm of the precursor powder A;
(4) Taking 100g of precursor powder A, stirring and dispersing in 100ml of ethanol, then adding 40ml of aluminum isopropoxide solution, and continuing stirring for about 20 hours under the condition of 60 ℃ water bath until the solvent is completely evaporated to obtain precursor powder B;
(5) Placing the precursor powder B in a corundum sagger, placing the sagger in a box-type furnace, sintering for 28h at 980 ℃ in the air atmosphere, naturally cooling, crushing and screening the obtained product to obtain Al 2 O 3 Coated Al doped NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Example 3
The sodium ion battery cathode material comprises a core body and a coating layer coating the core body, wherein a doping layer is arranged between the core body and the coating layer, and the core body is NaNi 2/9 Fe 1/3 Mn 1/3 Cu 1/9 O 2 The coating layer is Nb 2 O 5 The doped layer being Nb, called Nb 2 O 5 Coated Nb doped NaNi 2/9 Fe 1/3 Mn 1/3 Cu 1/9 O 2 。
The preparation method of the positive electrode material of the sodium-ion battery comprises the following steps:
(1) Stirring and dispersing 38.2g of copper oxide, 115.5g of ferric oxide, 136.3g of manganese oxide, 71.7g of nickel oxide and 240.1g of sodium carbonate in 3000mL of deionized water to prepare slurry;
(2) Pumping the slurry into a sand mill, and performing sand milling treatment for 1h to control the granularity of the slurry to be about D50=500nm and about D90=900nm so as to obtain precursor slurry;
(3) Conveying the precursor slurry into a drying tower in a centrifugal spray dryer through a peristaltic pump, and instantaneously evaporating a solvent to obtain precursor powder A, wherein the granularity D50=12 μm of the precursor powder A;
(4) Taking 100g of precursor powder A, stirring and dispersing in 100ml of ethanol, then adding 40ml of niobium oxalate solution, and continuing stirring for about 20 hours under the condition of 50 ℃ water bath until the solvent is completely evaporated to obtain precursor powder B;
(5) Placing the precursor powder B in a corundum sagger, placing the sagger in a box-type furnace, sintering for 28h at 980 ℃ in the air atmosphere, naturally cooling, crushing and screening the obtained product to obtain Nb 2 O 5 Coated Nb doped NaNi 2/9 Fe 1/ 3 Mn 1/3 Cu 1/9 O 2 。
Example 4
The positive electrode material of the sodium-ion battery comprises a core body and a coating layer coating the core body, wherein a doping layer is arranged between the core body and the coating layer, and the core body is NaNi 1/3 Mn 2/3 O 2 The coating layer is ZrO 2 Mixing ofThe impurity layer being Zr, called ZrO 2 Coated Zr-doped NaNi 1/3 Mn 2/3 O 2 。
The preparation method of the positive electrode material of the sodium-ion battery comprises the following steps:
(1) 23.67g nickel oxide, 57.96g manganese oxide, 26.5g sodium carbonate and 42.5g sodium nitrate are stirred and dispersed in 3000mL ethanol to prepare slurry;
(2) Pumping the slurry into a sand mill, and performing sand milling treatment for 1h to control the granularity of the slurry to be about D50=100nm and about D90=300nm to obtain precursor slurry;
(3) Conveying the precursor slurry into a drying tower in a centrifugal spray dryer through a peristaltic pump, and instantaneously evaporating a solvent to obtain precursor powder A, wherein the granularity D50=6 μm of the precursor powder A;
(4) Taking 100g of precursor powder A, stirring and dispersing in 100ml of isopropanol, then adding 30ml of zirconium carbonate solution, and continuing stirring for about 18 hours under the condition of 120 ℃ water bath until the solvent is completely evaporated to obtain precursor powder B;
(5) Placing the precursor powder B in a corundum sagger, placing the sagger in a box-type furnace, sintering for 22h at 800 ℃ in the air atmosphere, naturally cooling, crushing and screening the obtained product to obtain ZrO 2 Coated Zr doped NaNi 1/3 Mn 2/3 O 2 。
Example 5
The sodium ion battery cathode material comprises a core body and a coating layer coating the core body, wherein a doping layer is arranged between the core body and the coating layer, and the core body is NaNi 1/3 Co 1/3 Mn 1/3 O 2 The cladding layer is CdO, the doping layer is Cd, and the doping layer is Cd and is named as Cd-coated Cd doped NaNi 1/3 Co 1/3 Mn 1/3 O 2 。
The preparation method of the positive electrode material of the sodium-ion battery comprises the following steps:
(1) Stirring and dispersing 74.7g of nickel oxide, 74.9g of cobalt oxide, 86.9 g of manganese oxide and 158.9g of sodium carbonate in 3000mL of ethanol to prepare slurry;
(2) Pumping the slurry into a sand mill, and performing sand milling treatment for 1h to control the particle size of the slurry to be about D50=300nm and D90=700nm so as to obtain precursor slurry;
(3) Conveying the precursor slurry into a drying tower in a centrifugal spray dryer through a peristaltic pump, and instantaneously evaporating a solvent to obtain precursor powder A, wherein the granularity D50=16 μm of the precursor powder A;
(4) Taking 100g of precursor powder A, stirring and dispersing in 100ml of isopropanol, then adding 30ml of dimethyl cadmium solution, and continuing stirring for about 18 hours under the condition of 80 ℃ water bath until the solvent is completely evaporated to obtain precursor powder B;
(5) Placing the precursor powder B in a corundum sagger, placing the sagger in a box-type furnace, sintering for 20h at 800 ℃ in the air atmosphere, naturally cooling, crushing and screening the obtained product to obtain the Cd-doped NaNi coated with CdO 1/3 Co 1/ 3 Mn 1/3 O 2 。
Example 6
The positive electrode material of the sodium-ion battery comprises a core body and a coating layer coating the core body, wherein a doping layer is arranged between the core body and the coating layer, and the core body is NaNi 2/5 Fe 1/5 Mn 2/5 O 2 The cladding layer is MgO and the doped layer is Mg, which is called MgO-coated Mg-doped NaNi 2/5 Fe 1/5 Mn 2/5 O 2 。
The preparation method of the positive electrode material of the sodium-ion battery comprises the following steps:
(1) Stirring and dispersing 29.7g of nickel oxide, 15.9g of ferric oxide, 34.78 g of manganese oxide and 52.9g of sodium carbonate in 2000mL of ethanol to prepare slurry;
(2) Pumping the slurry into a sand mill, and performing sand milling treatment for 1h to control the granularity of the slurry to be about D50=200nm and about D50=500nm to obtain precursor slurry;
(3) Conveying the precursor slurry into a drying tower in a centrifugal spray dryer through a peristaltic pump, and instantaneously evaporating a solvent to obtain precursor powder A, wherein the granularity D50=12 μm of the precursor powder A;
(4) Taking 100g of precursor powder A, stirring and dispersing in 100ml of N-methyl pyrrolidone, then adding 30ml of magnesium citrate solution, and continuing stirring for about 16 hours under the condition of 90 ℃ water bath until the solvent is completely evaporated to obtain precursor powder B;
(5) Placing the precursor powder B in a corundum sagger, placing the sagger in a box-type furnace, sintering at 700 ℃ for 24 hours in the air atmosphere, naturally cooling, crushing and screening the obtained product to obtain the MgO-coated Mg-doped NaNi 2/5 Fe 1/ 5 Mn 2/5 O 2 。
Example 7
This example was prepared in the same manner as example 1 except that the zirconium n-butoxide solution was added in step (4) of example 1, and the dimethylaluminum solution was added in step (4) of this example, with the remainder being the same.
Example 8
The preparation method of this example is the same as that of example 1 except that the zirconium n-butoxide solution is added in step (4) of example 1, and the niobium oxalate solution is added in step (4) of this example, the rest being the same.
Example 9
The preparation method of this example is the same as that of example 1, except that the zirconium n-butoxide solution is added in step (4) of example 1, and the titanium tetraisopropoxide solution is added in step (4) of this example, the rest being the same.
Comparative example 1
The preparation method of the positive electrode material of the sodium-ion battery in the comparative example comprises the following steps:
(1) Stirring and dispersing 74.7g of nickel oxide, 79.8g of iron oxide, 86.9 g of manganese oxide and 158.9g of sodium carbonate in 3000mL of deionized water to prepare slurry;
(2) Pumping the slurry into a sand mill, and performing sand milling treatment for 1h to control the granularity of the slurry to be about D50=500nm and D90=1.2 μm so as to obtain precursor slurry;
(3) Conveying the precursor slurry into a drying tower in a centrifugal spray dryer through a peristaltic pump, and instantaneously evaporating a solvent to obtain precursor powder A, wherein the granularity D50=10 μm of the precursor powder A;
(4) Taking precursor powder APlacing 100g of corundum sagger in a box furnace, sintering the sagger for 25h at 900 ℃ in the air atmosphere, naturally cooling, crushing and screening the obtained product to obtain the layered metal oxide NaNi 1/ 3 Fe 1/3 Mn 1/3 O 2 。
Comparative example 2
The comparative example is substantially the same as example 1, except that in example 1, the precursor slurry is conveyed into a drying tower in a centrifugal spray dryer through a peristaltic pump, and the solvent is instantaneously evaporated to obtain precursor powder a, wherein the particle size D50=10 μm; in contrast, in comparative example 2, the precursor slurry was evaporated and dried to obtain precursor powder a.
The positive electrode materials prepared in example 1 and comparative example 1 are subjected to sample morphology observation and analysis by a scanning electron microscope, and the results are respectively shown in fig. 2 and fig. 3, wherein fig. 2 is the morphology of the positive electrode material of example 1 of the invention, fig. 3 is the morphology of the positive electrode material of comparative example 1, and it can be seen from comparison between fig. 2 and fig. 3 that the particles of the coated positive electrode material are smoother and more complete and have higher sphericity.
The positive electrode materials of the sodium-ion batteries obtained in examples 1 to 3 and comparative example 1 were uniformly slurried with an adhesive (polyvinylidene fluoride PVDF was dissolved in N-methylpyrrolidone NMP, the content of PVDF was 3.5%) and a conductive agent (conductive carbon black SP) in a weight ratio of 8 6 And (3) dissolving the electrolyte into a mixture of Propylene Carbonate (PC) and Ethylene Carbonate (EC), and carrying out buckling assembly and assembly on the positive electrode shell in sequence, sealing the assembled buckling battery by using a sealing machine, and then carrying out electrochemical performance test on the battery by using a new Velcro test cabinet, wherein the electrochemical data are shown in Table 1.
TABLE 1 electrochemical Performance testing of the examples and comparative examples
From the results in table 1, it can be seen that the first coulombic efficiency of the positive electrode materials of the sodium-ion batteries of examples 1 to 3 can reach 90% or more, and the capacity retention rate after 500 cycles is 90% or more, while the positive electrode material of the sodium-ion battery of comparative example 1, which is not subjected to coating doping modification, only has 75.1% of capacity retention rate after 500 cycles. The coating layer is used as a protection unit and does not participate in the redox reaction in the charging and discharging process, so that the volume change stress of the whole material in the circulating process can be reduced, and the circulating stability and the capacity retention rate are improved; at the same time, in the process of high-temperature sintering, the coating layer M y O z The metal ion M in (A) is further converted to Na x M1 a M2 b M3 c O 2 The doping is realized by the internal diffusion and permeation of the anode material; namely, the coating doping double modification is realized simultaneously by a one-step sintering method, and on one hand, the Na is doped x M1 a M2 b M3 c O 2 M in (1) can relieve Na in the charge-discharge process x M1 a M2 b M3 c The O crystal structure changes, the stability of the crystal in the circulating process is improved, on the other hand, the coating layer and the core body do not have obvious layer boundaries due to the doping mode, the coating layer and the core body are combined more tightly, the structural stability is improved, and the capacity retention rate of the anode material in the circulating process is further improved.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it is not limited to the embodiments, and those skilled in the art should understand that the technical solutions of the present invention can be modified or substituted with equivalents without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The positive electrode material of the sodium ion battery is characterized by comprising a core body and a coating layer coating the core body, wherein a doping layer is arranged between the core body and the coating layer, the core body is a layered metal oxide, the coating layer is a metal oxide, and metal ions in the coating layer penetrate into the core body to be doped to form the doping layer.
2. The positive electrode material for sodium-ion batteries according to claim 1, wherein the layered metal oxide has a structural formula of Na x M1 a M2 b M3 c O 2 Wherein M1, M2 and M3 are transition metal elements, x is more than or equal to 0.2 and less than or equal to 1, a + b + c =1, a is more than or equal to 0 and less than or equal to 1,0 and less than or equal to b is more than or equal to 1,0 and less than or equal to c is less than or equal to 1.
3. The positive electrode material for sodium-ion batteries according to claim 2, wherein said M1, said M2, and said M3 each independently comprise at least one of Ni, fe, mn, co, cu, cr, and V.
4. The positive electrode material for sodium-ion battery according to claim 1, wherein the metal oxide has a structural formula of M y O z Wherein M comprises at least one of Ge, rb, cd, zn, zr, mg, al, nb, ti, sn, ca, ru, mo, sb, sr and Ag, and y is more than 0 and less than or equal to 3,0 and z is more than or equal to 5.
5. The positive electrode material for sodium-ion battery according to claim 4, wherein the doping element of the doped layer is the metal oxide M y O z The metal M in (1).
6. The sodium-ion battery positive electrode material according to claim 1, characterized by comprising at least one of the following features (1) to (3):
(1) the thickness of the coating layer is 100nm to 1 mu m;
(2) the doping depth of the metal in the doping layer is 50-200 nm;
(3) the coating layer accounts for 0.1 to 7wt% of the total mass of the core body, the coating layer and the doping layer.
7. The preparation method of the positive electrode material of the sodium-ion battery is characterized by comprising the following steps:
(a) Mixing a sodium source, a metal source and a first solvent to prepare slurry, and preparing precursor powder A after sand grinding and spray granulation of the slurry;
(b) Adding the precursor powder A into a second solvent, heating and stirring, adding a solution containing metal M, and removing the second solvent to obtain precursor powder B;
(c) And sintering the precursor powder B under the atmosphere with a certain oxygen content, and then cooling and grinding to obtain the metal M-doped sodium-ion battery positive electrode material coated by the oxide of the metal M.
8. The method of claim 7, wherein the metal source comprises at least one of a M1 metal source, a M2 metal source, and a M3 metal source, and wherein the M1 metal source, the M2 metal source, and the M3 metal source are all derived from a transition metal element.
9. The method of claim 8, wherein the M1 metal source, the M2 metal source, and the M3 metal source each independently comprise at least one of nickel oxide, iron oxide, manganese oxide, cobalt oxide, copper oxide, chromium oxide, and vanadium oxide.
10. The method for producing a positive electrode material for a sodium-ion battery according to claim 7, characterized by comprising at least one of the following features (1) to (12):
(1) In step (a), the sodium source comprises at least one of sodium carbonate, sodium bicarbonate, sodium nitrate, and sodium hydroxide;
(2) In the step (a), the first solvent is at least one selected from deionized water, ethanol, methanol, isopropanol, triethylene glycol, polyethylene glycol, acetone, N-methylpyrrolidone, N-N dimethylformamide, acetone, acetonitrile and diethyl ether;
(3) The granularity of the slurry after sanding treatment is controlled to be not less than 50nm and not more than 1 mu m of D50, not less than 200nm and not more than 2 mu m of D90;
(4) The granularity of the precursor powder A is more than or equal to 1 mu m and less than or equal to D50 and less than or equal to 20 mu m;
(5) In the step (b), the second solvent is at least one selected from the group consisting of ethanol, methanol, isopropanol, triethylene glycol, polyethylene glycol, acetone, N-methylpyrrolidone, N-N dimethylformamide, acetone, acetonitrile and diethyl ether;
(6) In the step (b), the heating and stirring temperature is 30 to 100 ℃;
(7) In the step (b), the heating and stirring time is 8-24 h;
(8) In the step (c), the sintering temperature is 600 to 1000 ℃;
(9) In the step (c), the sintering time is 10 to 25 hours;
(10) In the step (c), the oxygen content atmosphere is gas with 20 to 80 percent of oxygen content;
(11) In the step (c), the flow rate of the oxygen content atmosphere is 1L/min to 20L/min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115872463A (en) * | 2023-02-24 | 2023-03-31 | 江门市科恒实业股份有限公司 | Method for preparing layered positive electrode material of sodium ion battery and sodium ion positive electrode material |
| CN116443946A (en) * | 2023-03-15 | 2023-07-18 | 深圳市比克动力电池有限公司 | Positive electrode material, preparation method thereof and battery |
| CN116525813A (en) * | 2023-06-27 | 2023-08-01 | 宁波容百新能源科技股份有限公司 | Layered oxide, preparation method thereof and sodium ion battery positive electrode plate |
| CN117080537A (en) * | 2023-09-25 | 2023-11-17 | 三一红象电池有限公司 | Battery positive electrode material and sodium ion battery containing same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115872463A (en) * | 2023-02-24 | 2023-03-31 | 江门市科恒实业股份有限公司 | Method for preparing layered positive electrode material of sodium ion battery and sodium ion positive electrode material |
| CN116443946A (en) * | 2023-03-15 | 2023-07-18 | 深圳市比克动力电池有限公司 | Positive electrode material, preparation method thereof and battery |
| CN116525813A (en) * | 2023-06-27 | 2023-08-01 | 宁波容百新能源科技股份有限公司 | Layered oxide, preparation method thereof and sodium ion battery positive electrode plate |
| CN116525813B (en) * | 2023-06-27 | 2023-10-27 | 宁波容百新能源科技股份有限公司 | Layered oxide, preparation method thereof and sodium ion battery positive electrode plate |
| CN117080537A (en) * | 2023-09-25 | 2023-11-17 | 三一红象电池有限公司 | Battery positive electrode material and sodium ion battery containing same |
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