CN115676915A - Layered oxide positive electrode material and preparation method and application thereof - Google Patents
Layered oxide positive electrode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN115676915A CN115676915A CN202211351217.8A CN202211351217A CN115676915A CN 115676915 A CN115676915 A CN 115676915A CN 202211351217 A CN202211351217 A CN 202211351217A CN 115676915 A CN115676915 A CN 115676915A
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- China
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- layered oxide
- sodium
- sintering
- preparation
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- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- 239000007774 positive electrode material Substances 0.000 title claims description 26
- 238000005245 sintering Methods 0.000 claims abstract description 70
- 239000010406 cathode material Substances 0.000 claims abstract description 68
- 239000000463 material Substances 0.000 claims abstract description 65
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- 239000000203 mixture Substances 0.000 claims abstract description 48
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 38
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Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a layered oxide anode material, a preparation method and application thereof, wherein the layered oxide anode material is NaxMO 2 X is more than 0 and less than or equal to 1, M is selected from any one or the combination of at least two of Ni, co, mn, fe, cu, ti and Sn; the preparation method comprises the following steps: mixing a sodium source, an M metal source and a carbon-containing material to obtain a mixture; and sintering the mixture under an aerobic condition to obtain the layered oxide cathode material. The invention regulates and controls the oxygen distribution on the surface of the layered oxide through the design and the synergistic action of the raw materials and the process method to form an oxygen-poor stable phase, and the obtained layered oxide anode material has a structure gradually transited from inside to outside and has excellent performanceStructural integrity, stability and electrochemical performance, and can effectively improve the rate capability and the cycle performance of the battery. The preparation method has simple process route, is easy to realize large-scale production, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of sodium-ion battery materials, and particularly relates to a layered oxide anode material and a preparation method and application thereof.
Background
With the development and progress of energy technology, lithium batteries have been widely applied to the fields of energy storage, electric vehicles, consumer electronics and the like, and become an indispensable component in the life of people at present. However, due to the limited reserves of the common resources of lithium batteries such as lithium and nickel, the price of the raw materials of the lithium batteries is continuously increased in recent years, so that the cost performance of the lithium batteries is seriously reduced, and the application of the lithium batteries is influenced. In addition, due to the continuous pursuit of energy density of lithium batteries, the safety of lithium batteries is also a considerable problem.
Sodium batteries are an important branch of energy technology, and compared with lithium batteries, the reserve of sodium is far higher than that of lithium, and with the continuous maturation of the technologies of extracting sodium from seawater and the like, the price of sodium can also go on to be lowered, which is also the inherent advantage of the price of sodium batteries. Moreover, the lithium battery is easy to generate dendrite and the like, so that the potential safety hazard of short circuit spontaneous combustion is caused, and the sodium battery is difficult to form dendrite and has higher safety than the lithium battery. In comprehensive consideration, although the energy density and the power density of the sodium battery are lower than those of the lithium battery, the sodium battery still has a plurality of specific advantages, and the sodium battery has great potential to fill the market gap between the lithium battery and the lead-acid battery. Currently, the negative electrode materials commercialized for sodium batteries mainly include hard carbon, and the positive electrode materials mainly include prussian, polyanion, oxides, and the like; among them, the oxide-based positive electrode material has high theoretical capacity, simple structure, and easy synthesis, and has been drawing attention in the industry.
Transition metal layered oxides are a representative group of oxide-based positive electrode materials, and nickel manganese-based layered oxides are more attractive. Similar to the high-nickel oxide anode material in the lithium battery, the gram capacity of the layered oxide has a direct relation with the content of Ni in the layered oxide, and the specific capacity of the oxide anode material can be effectively improved by increasing the content of Ni. However, during cycling, too high a Ni contentThe structural stability of the layered oxide is directly affected. Due to Ni 4+ The material has higher activity in the electrolyte, and when the Ni content is higher than 60%, the cycling stability of the material is obviously reduced. In addition, when the voltage is higher than 4.0V, a series of side reactions occurring between the layered oxide and the electrolyte further accelerate the degradation of the material properties.
In order to improve the performance defect of the nickel-manganese-based layered oxide, an attempt is made to construct a coating layer on the surface of the layered oxide material, so that the electrolyte can be separated from the layered oxide, and the electrolyte and the layered oxide are prevented from being in direct contact, thereby reducing the occurrence of side reactions, and playing roles in inhibiting phase change and improving the structural stability of the material. For example, CN113889613A discloses a layered sodium-ion battery cathode material with a gradient structure, and the preparation method thereof includes: uniformly mixing a layered oxide positive electrode material with a P2 phase structure with a magnesium source, and reacting Mg by using a low-temperature molten salt method 2+ Diffusing into the layered oxide to form a layered oxide with a MgO coating layer and a gradient Mg 2+ A doped layered oxide positive electrode material; na in Mg-rich layered oxide formed in low-temperature molten salt process due to surface layer + The concentration is relatively low and thus tends to form a surface layer of a P3 phase structure and a core layer of a P2 phase structure. CN114613981A discloses a zinc-doped and zinc-oxide-coated manganese-based layered oxide material, which is prepared by ball-milling and mixing a sodium source, a nickel source, a copper source, a zinc source and a manganese source according to a certain stoichiometric ratio, and then calcining at a high temperature, so that zinc ions in the obtained product exist in a bulk phase structure of a P2-type layered oxide and are uniformly enriched on the particle surface of the P2-type layered oxide in a form of zinc oxide, and the electrochemical performance of the P2-type nickel-manganese-based layered oxide anode material is improved. CN109638273A discloses a coating method for a sodium ion battery positive electrode material, which first uniformly mixes a layered oxide positive electrode material, a coating precursor and a solvent, then performs spray drying to obtain a positive electrode material coated by the coating precursor, and then performs secondary sintering on the above materials to form an oxide shell, thereby obtaining an oxide-coated layered oxide positive electrode material; wherein the coating precursor is oxide, nitrate and hydrate thereof, sulfate and hydrate thereof of Al, mg, ti, zn, zr, nb or LaOne or more of substance and organic salt.
Generally, in the current layered oxide cathode material, the material often used as the coating layer includes metal oxides such as aluminum oxide, magnesium oxide, titanium oxide, zinc oxide, etc., and the common coating manner includes a chemical method, a ball milling method, an atomic layer deposition technique, etc. The sodium electrode anode material has high sensitivity to moisture, so that the application of a coating method is limited, and the coating is usually finished by sintering for many times, thereby bringing high preparation difficulty and processing cost. Moreover, since the coating layer material and the layered oxide cathode material have different compositions and structures, the introduction of the coating layer will inevitably introduce the problem of the interface between the coating layer and the cathode material, which affects the ionic conductivity of the material. In addition, due to different material structures, the coating layer and the layered oxide cathode material are difficult to keep the same expansion coefficient in the charging and discharging processes, so that the coating layer is damaged or falls off, and the performance of the sodium battery is influenced.
Therefore, there is a need in the art to develop sodium cathode materials with better electrochemical properties, especially better stability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a layered oxide cathode material and a preparation method and application thereof, wherein the surface of the obtained layered oxide cathode material forms an oxygen-deficient structure through the design of raw materials, particularly carbon-containing materials, and the mutual cooperation of the raw materials and a specific process, so that the in-situ modification and the coating of the layered oxide are realized. The layered oxide positive electrode material has excellent electrochemical performance, structural integrity and stability, so that the rate capability and the cycle performance of the sodium ion battery are improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a layered oxide cathode material, wherein the layered oxide cathode material is NaxMO 2 Wherein x is more than 0 and less than or equal to 1, M is selected from any one or the combination of at least two of Ni, co, mn, fe, cu, ti and Sn; the preparation method comprises the following steps: mixing a sodium source, a M metal source andmixing carbonaceous materials to obtain a mixture; and sintering the mixture under an aerobic condition to obtain the layered oxide cathode material.
In the preparation method of the layered oxide cathode material, the carbon-containing material is introduced at the mixing stage of the sodium source and the M metal source to obtain a mixture comprising a precursor (the sodium source and the M metal source) and a carbon-containing material composite structure. During the sintering process of the mixture, the carbon-containing material is subjected to a series of carbonization and oxidation reactions, oxygen is taken away from the surface of a precursor in a short time, and the rapid loss of oxygen in the structure is caused, so that the rapid loss of the surface oxygen of the layered oxide prepared from the sodium source and the M metal source leads to the phase change of the layered oxide from the layered structure to the rock salt phase, the gradual transition of the structure from the layered oxide to the rock salt phase from inside to outside is realized, and the surface of the material in the obtained layered oxide anode material has a stable oxygen-poor structure, namely an oxygen-poor coating layer is formed, and the coating layer is synchronously formed in the process of forming the layered oxide from the sodium source and the M metal source and has the characteristics of in-situ modification/coating; more importantly, the coating layer and the body material (bulk phase) of the layered oxide have the same components, the structure is gradually transited from inside to outside, and the coating layer is tightly combined with the body (bulk phase) of the layered oxide, so that the generation of an interface is reduced. Meanwhile, the rock salt phase generated in situ is an oxygen-deficient structure, so that further loss of oxygen in the oxide can be prevented, and the thickness of the phase change layer can be controlled within the range of about 10 nm; in addition, in the preparation process, the rock salt phase generated by sintering can reduce the continuous generation of oxygen defects in the oxide and improve the structural integrity of the target product.
In the invention, the design of raw materials, particularly the introduction of a carbon-containing material, is matched with a specific process method, the oxygen distribution condition of the surface of the layered oxide is regulated and controlled, and an oxygen-poor stable phase is formed, so that a coating layer which is the same as the components of the bulk material, tightly combined and structurally stable is generated in situ, the obtained layered oxide anode material has a structure gradually transited from inside to outside, the interface problem and the coating layer damage and shedding problem caused by conventional coating are avoided, and the structure integrity, the stability and the electrochemical performance are excellent. The preparation method has the advantages of wide raw material source, no need of harsh reaction conditions and complex preparation steps, simple process route, easy realization of large-scale production and wide application prospect.
Preferably, the sodium source comprises sodium hydroxide and/or sodium salt.
Preferably, the sodium source comprises any one of sodium hydroxide, sodium carbonate, sodium acetate, sodium sulfate, sodium nitrate, sodium chloride or a combination of at least two thereof.
In the invention, M in the M metal source is NaxMO 2 M in (2) is any one or the combination of at least two of Ni, co, mn, fe, cu, ti and Sn; the M metal source is selected from any one of a nickel source, a manganese source, an iron source, a cobalt source, a copper source, a titanium source and a tin source or a combination of at least two of the nickel source, the manganese source, the iron source, the cobalt source, the copper source, the titanium source and the tin source.
Preferably, the M metal source comprises a nickel source and a manganese source, and at least one of an iron source, a cobalt source, a copper source, a titanium source and a tin source; thus, a nickel-manganese-based layered oxide positive electrode material can be obtained.
Further preferably, the M metal source comprises a combination of a nickel source, a manganese source, and an iron source.
Preferably, the nickel source comprises nickel oxide NiO, nickel hydroxide Ni (OH) 2 And a nickel salt, or a combination of at least two thereof.
Preferably, the nickel salt comprises any one of nickel nitrate, nickel sulfate, nickel carbonate and nickel acetate or the combination of at least two of the nickel nitrate, the nickel sulfate, the nickel carbonate and the nickel acetate; the nickel salt optionally contains bound water.
Preferably, the manganese source comprises an oxide and/or salt of manganese.
Preferably, the manganese oxide comprises MnO, mnO 2 、Mn 2 O 3 、Mn 3 O 4 Any one or a combination of at least two of them.
Preferably, the manganese salt comprises any one of manganese carbonate, manganese sulfate, manganese chloride and manganese nitrate or a combination of at least two of the manganese carbonate, the manganese sulfate, the manganese chloride and the manganese nitrate; the manganese salt optionally contains bound water.
Preferably, the iron source comprises any one of iron oxide, iron salt (ferric salt), ferrous salt (ferrous salt), or a combination of at least two thereof.
Preferably, the iron oxide comprises FeO, fe 2 O 3 、Fe 3 O 4 Or a combination of at least two thereof.
Preferably, the iron salt comprises any one of iron nitrate, iron phosphate, iron carbonate or a combination of at least two thereof.
Preferably, the ferrous salt comprises any one of ferrous sulfate, ferrous oxalate, ferrous phosphate, ferrous nitrate and ferrous carbonate or a combination of at least two of the two.
In the invention, the sodium source and the M metal source are respectively used in the amount of the target product NaxMO 2 The stoichiometric ratio of Na to M in the mixture was determined.
Preferably, the sodium source may be added in excess relative to the M metal source.
Preferably, the actual amount of the sodium source is 101-113%, for example 102%, 103%, 104%, 105%, 107%, 109%, 110% or 112% based on 100% of the theoretically required sodium source, and the specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the range, and more preferably 101-105%, for reasons of brevity and conciseness.
Preferably, the carbonaceous material comprises any one of or a combination of at least two of a carbohydrate, polystyrene, polydopamine.
Preferably, the saccharide compound comprises any one of glucose, sucrose, chitosan, maltose, starch or a combination of at least two thereof.
Preferably, the mass of the carbonaceous material is 0.2 to 5.5%, for example, 0.3%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5% based on 100% of the mass of the layered oxide made of the sodium source and the M metal source (i.e., the theoretical mass of the layered oxide), and specific points between the above points are not exhaustive, and for reasons of brevity, the present invention does not list the specific points included in the range, and more preferably 1 to 5%.
As a preferred technical scheme of the invention, the theoretical mass of the layered oxide obtained by calculation according to the using amounts of the sodium source and the M metal source is 0.2-5.5%, and more preferably 1-5% in terms of 100% of the theoretical mass of the layered oxide, so that the carbonaceous material generates a series of carbonization and oxidation reactions in the subsequent sintering process, the oxygen distribution on the surface of the layered oxide material is effectively regulated, and an oxygen-poor stable phase is formed on the surface, so that a coating layer with the same component, different structure, close combination and stable structure as a layered oxide body (bulk phase) is generated in situ, and the layered oxide cathode material has excellent structural integrity, stability and electrochemical performance. If the quality of the carbon-containing material is too low, the oxygen distribution cannot be effectively regulated, the inherent defects of the layered oxide anode material are not obviously improved, and the structural stability and the cycle performance of the obtained anode material are still poor; if the quality of the carbonaceous material is too high, the thickness of the formed protective layer is too large, the electrochemical performance of the cathode material is influenced, excessive sodium carbonate is formed on the surface, and the processing performance of the cathode material is directly influenced by too high residual alkali.
Preferably, in the mixing, the sodium source and the M metal source are initially mixed, and then the carbonaceous material is added and mixed.
Preferably, the method of mixing is ball milling, further preferably wet ball milling.
Preferably, the ball milling is carried out in the presence of an organic solvent (wet ball milling), which includes an alcohol solvent and/or a ketone solvent.
Preferably, the alcohol solvent includes any one of methanol, ethanol, n-propanol, isopropanol or a combination of at least two thereof, and further preferably ethanol.
Preferably, the ketone solvent includes acetone and/or methyl ethyl ketone, further preferably acetone.
Preferably, the ball-to-material ratio of the ball mill is (0.5-2): 1, and can be, for example, 0.6.
Preferably, the rotational speed of the ball mill is 100-350rpm, for example, 120rpm, 150rpm, 180rpm, 200rpm, 220rpm, 250rpm, 280rpm, 300rpm, 320rpm or 340rpm, and specific points therebetween, for brevity and conciseness, the present invention is not exhaustive of the specific points included in the ranges.
Preferably, the ball milling time is 1-5h, for example, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h or 4.5h, and the specific values therebetween are not exhaustive for the sake of brevity and clarity.
Preferably, the method further comprises a drying step after the ball milling is finished.
Preferably, the drying temperature is 60-100 ℃, for example, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ or 95 ℃, and the specific values therebetween are not exhaustive, and for brevity and conciseness, the invention is not intended to be limited to the specific values included in the ranges.
Preferably, the drying time is 1-6h, for example 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h or 5.5h, and specific values therebetween, not to be limited by space and for the sake of brevity, the invention is not exhaustive of the specific values included in the ranges.
Preferably, the sintering is performed in an air atmosphere.
In the present invention, the sintering is carried out in any apparatus known in the art in which sintering can occur, preferably the apparatus for sintering comprises a muffle furnace, a tube furnace, a rotary furnace, a box furnace, a pusher kiln or a roller kiln.
Preferably, the sintering comprises a first stage sintering and a second stage sintering which are carried out in sequence, wherein the temperature of the first stage sintering is lower than that of the second stage sintering.
Preferably, the temperature of the first stage sintering is 300-600 ℃, for example, 320 ℃, 350 ℃, 380 ℃, 400 ℃, 420 ℃, 450 ℃, 480 ℃, 500 ℃, 520 ℃, 550 ℃ or 580 ℃, and specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not intended to be limited to the specific values included in the scope.
Preferably, the first sintering period is 2-7h, for example, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h or 6.5h, and the specific values therebetween are not limited by the space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the temperature of the second stage sintering is 800-950 ℃, and may be, for example, 810 ℃, 830 ℃, 850 ℃, 870 ℃, 890 ℃, 900 ℃, 920 ℃ or 940 ℃, and specific values therebetween are not exhaustive for the invention and are included in the scope for brevity.
Preferably, the second sintering time is 10-30h, for example, 11h, 13h, 15h, 17h, 19h, 20h, 21h, 23h, 25h, 27h or 29h, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not limited to the specific values included in the range.
Preferably, the preparation method comprises the following steps:
(1) Mixing a sodium source, an M metal source and a carbon-containing material through wet ball milling, and drying after uniform mixing to obtain a mixture;
wherein the M metal source comprises a nickel source, a manganese source and any one of an iron source, a cobalt source, a copper source, a titanium source and a tin source; the carbon-containing material comprises any one or a combination of at least two of carbohydrate, polystyrene and polydopamine; the mass of the carbon-containing material is 0.2-5.5% by taking the mass of the layered oxide prepared from the sodium source and the M metal source as 100%;
the ball-material ratio of the wet ball milling is (0.5-2) to 1, the rotating speed is 100-350rpm, and the time is 1-5h;
(2) Sequentially carrying out first-stage sintering and second-stage sintering on the mixture obtained in the step (1) under an aerobic condition to obtain the layered oxide cathode material;
wherein the temperature of the first-stage sintering is 300-600 ℃, and the time is 2-7h; the temperature of the second-stage sintering is 800-950 ℃, and the time is 10-30h.
In a second aspect, the present invention provides a layered oxide positive electrode material prepared by the preparation method according to the first aspect.
The layered oxide anode material is NaxMO 2 Wherein M is selected from any one or the combination of at least two of Ni, co, mn, fe, cu, ti and Sn.
Where 0 < x.ltoreq.1, x may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9 or 0.95, and specific values therebetween, not to be exhaustive of the specific values included in the range for brevity and conciseness.
Preferably, x is 0.5 to 1, preferably 0.5 < x.ltoreq.1, more preferably 0.6 < x.ltoreq.1.
Preferably, the layered oxide cathode material is NaxNiyMnzM' (1-y-z) O 2 (ii) a M' is selected from any one or the combination of at least two of Co, fe, cu, ti and Sn; thus, the layered oxide positive electrode material is a nickel-manganese-based layered oxide positive electrode material.
Wherein 0 < y < 1, y can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85 or 0.9, and the specific values therebetween, are not exhaustive and for brevity, the invention does not include the specific values included in the ranges, and further preferably 0 < y ≦ 0.5.
0 < z < 1, z can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, or 0.9, and specific values therebetween, for brevity and clarity, are not intended to be exhaustive of the invention to include specific values within the stated range, and more preferably 0 < z ≦ 0.5.
0＜y+z≤1。
Preferably, the layered oxide cathode material is NaxNiyMnzFe (1-y-z) O 2 。
The invention adopts the optimized design of the preparation methodEffectively regulating and controlling the surface oxygen distribution of the layered oxide, modifying a layered structure within the thickness of about 10nm of the surface, and forming an oxygen-deficient stable phase on the surface of the material, namely forming a homogeneous oxygen-deficient coating layer; the coating layer and the layered oxide body have the same components and different structures, so that the problem of poor ionic conductivity caused by interface problems is solved; and the structure of the coating layer is stable, the coating layer can not be damaged or fall off, and the layered oxide can be continuously protected. The layered oxide positive electrode material has a structure gradually transited from inside to outside, has excellent structural integrity and stability, and has excellent ionic conductivity and capacity and excellent electrochemical performance; the layered oxide cathode material NaxMO 2 The preferred x in (1) is 0.65-1 (P2 phase with x of about 0.67-0.7, O3 phase with x of about 0.7-1), and the higher sodium content provides sufficient Na + To perform electrochemical reaction, so that the sodium ion battery containing the electrochemical reaction has excellent capacity and cycle performance.
Preferably, the specific capacity of the layered oxide cathode material at 0.1C is more than 122mAh/g, and can reach 122.8-124.1mAh/g.
Preferably, the specific capacity of the layered oxide cathode material at 0.5C is more than 118mAh/g, and can reach 118.5-120.9mAh/g.
Preferably, the specific capacity of the layered oxide cathode material at 1.0C is more than 109mAh/g, and can reach 109.3-115.0mAh/g.
Preferably, the specific capacity of the layered oxide cathode material at 2.0C is more than 92mAh/g, and can reach 92.4-101.3mAh/g.
Preferably, the specific capacity of the layered oxide cathode material at 5.0C is more than or equal to 79.5mAh/g, and can reach 79.5-84.1mAh/g.
In a third aspect, the present invention provides a use of the layered oxide cathode material according to the second aspect in an electrochemical device.
Preferably, the electrochemical device comprises a sodium ion battery or a capacitor.
In a fourth aspect, the present invention provides a sodium ion battery comprising a layered oxide positive electrode material according to the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the preparation method provided by the invention, through the design of raw materials, particularly the introduction of a carbon-containing material and the matching and synergistic effect of a specific process method, the oxygen distribution condition of the surface of the layered oxide is regulated and controlled to form an oxygen-deficient stable phase, and a coating layer which has the same components as a body material, different structures, tight combination and stable structure is generated in situ. The preparation method has the advantages of wide raw material source, simple process route, easy realization of large-scale production and wide application prospect.
(2) The layered oxide cathode material has excellent stability, specific capacity and rate capability, can be used for a sodium ion battery, can effectively improve the rate capability and cycle performance of the sodium ion battery, has a capacity retention rate of not less than 82.1% at a cycle of 100 cycles at 0.5C and a capacity retention rate of not less than 60% at a cycle of 300 cycles at 2.0C, and particularly has excellent cycle performance at high rate.
Drawings
Fig. 1 is an XRD pattern of the layered oxide cathode material provided in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
"optionally" or "either" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
The indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.
Reference throughout this specification to "one embodiment," "some embodiments," "exemplary," "specific examples" or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this document, schematic representations of the above terms are not necessarily intended to refer to the same embodiment or example.
In addition, the technical features according to the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
The raw materials involved in the following embodiments of the present invention are all commercially available products; among them, polystyrene (PS), available from Michelin (L815936, polystyrene microspheres, 0.05-0.1 μm); polydopamine was purchased from Xianqiyue biology under the brand number Q-0094192.
Example 1
A layered oxide cathode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Mixing Na 2 CO 3 、NiO、Fe 2 O 3 、Mn 2 O 3 Preliminary mixing was performed at a molar ratio of 1.545 2 CO 3 3% excess); adding polystyrene with the mass of 1% to the formed layered oxide by taking the theoretical mass of the layered oxide as 100%, and mixing by wet ball milling; the organic solvent adopted by the wet ball milling is ethanol (the mass ratio of solid matter to ethanol is 1.2), the ball-to-material ratio is 1; obtained by wet ball millingDrying the materials at 80 ℃ for 5 hours to obtain a mixture;
(2) Transferring the mixture obtained in the step (1) into a muffle furnace, sintering for 5h at 450 ℃ in an air atmosphere, heating to 900 ℃ and sintering for 20h to obtain a target product, namely the layered oxide anode material, wherein the theoretical chemical formula of the layered oxide anode material is NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Example 2
A layered oxide cathode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Mixing Na 2 CO 3 、NiO、Fe 2 O 3 、Mn 2 O 3 Preliminary mixing was carried out at a molar ratio of 1.545; adding polystyrene with the mass of 2% into the formed layered oxide by taking the theoretical mass of the layered oxide as 100%, and mixing by wet ball milling; the organic solvent adopted by the wet ball milling is acetone (the mass ratio of solid matters to acetone is 1.2), the ball-material ratio is 1; drying the material obtained by wet ball milling for 5 hours at the temperature of 70 ℃ to obtain a mixture;
(2) Transferring the mixture obtained in the step (1) to a muffle furnace, sintering for 5h at 450 ℃ in an air atmosphere, heating to 900 ℃ and sintering for 20h to obtain a target product, namely the layered oxide cathode material, wherein the theoretical chemical formula of the layered oxide cathode material is NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Example 3
A layered oxide cathode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Mixing Na 2 CO 3 、NiO、Fe 2 O 3 、Mn 2 O 3 Preliminary mixing was carried out at a molar ratio of 1.545; adding 3% by mass of polystyrene to the formed layered oxide, based on 100% by mass of the layered oxide, and mixing by wet ball milling; the organic solvent adopted by the wet ball milling is ethanol (the mass ratio of solid matter to ethanol is 1.2), the ball-material ratio is 1; ball prepared by wet methodDrying the ground material at 80 ℃ for 5 hours to obtain a mixture;
(2) Transferring the mixture obtained in the step (1) to a muffle furnace, sintering for 5h at 450 ℃ in an air atmosphere, heating to 900 ℃ and sintering for 20h to obtain a target product, namely the layered oxide cathode material, wherein the theoretical chemical formula of the layered oxide cathode material is NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Example 4
A layered oxide cathode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Na is mixed with 2 CO 3 、NiO、Fe 2 O 3 、Mn 2 O 3 Preliminary mixing is carried out at a molar ratio of 1.545; adding polystyrene with the mass of 4% into the formed layered oxide by taking the theoretical mass of the layered oxide as 100%, and mixing by wet ball milling; the organic solvent adopted by the wet ball milling is ethanol (the mass ratio of solid matter to ethanol is 1.2), the ball-to-material ratio is 1; drying the material obtained by wet ball milling at 80 ℃ for 5 hours to obtain a mixture;
(2) Transferring the mixture obtained in the step (1) to a muffle furnace, sintering for 5h at 450 ℃ in an air atmosphere, heating to 900 ℃ and sintering for 20h to obtain a target product, namely the layered oxide cathode material, wherein the theoretical chemical formula of the layered oxide cathode material is NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Example 5
A layered oxide cathode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Na is mixed with 2 CO 3 、NiO、Fe 2 O 3 、Mn 2 O 3 Preliminary mixing was carried out at a molar ratio of 1.545; adding polystyrene with the mass of 5 percent based on the theoretical mass of the formed layered oxide as 100 percent, and mixing by wet ball milling; the organic solvent adopted by the wet ball milling is ethanol (the mass ratio of solid matter to ethanol is 1.2), the ball-to-material ratio is 1;drying the material obtained by wet ball milling at 80 ℃ for 5 hours to obtain a mixture;
(2) Transferring the mixture obtained in the step (1) to a muffle furnace, sintering for 5h at 450 ℃ in an air atmosphere, heating to 900 ℃ and sintering for 20h to obtain a target product, namely the layered oxide cathode material, wherein the theoretical chemical formula of the layered oxide cathode material is NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Example 6
A layered oxide cathode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Na is mixed with 2 CO 3 、NiO、Fe 2 O 3 、Mn 2 O 3 Preliminary mixing was carried out at a molar ratio of 1.545; adding 6% by mass of polystyrene to the formed layered oxide, based on 100% by mass of the layered oxide, and mixing by wet ball milling; the organic solvent adopted by the wet ball milling is ethanol (the mass ratio of solid matter to ethanol is 1.2), the ball-to-material ratio is 1; drying the material obtained by wet ball milling at 80 ℃ for 5 hours to obtain a mixture;
(2) Transferring the mixture obtained in the step (1) into a muffle furnace, sintering for 5h at 450 ℃ in an air atmosphere, heating to 900 ℃ and sintering for 20h to obtain a target product, namely the layered oxide anode material, wherein the theoretical chemical formula of the layered oxide anode material is NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Example 7
A layered oxide cathode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Na is mixed with 2 CO 3 、NiO、Fe 2 O 3 、Mn 2 O 3 Preliminary mixing is carried out at a molar ratio of 1.55; adding polystyrene with the mass of 4.5 percent based on the theoretical mass of the formed layered oxide as 100 percent, and mixing by wet ball milling; the organic solvent adopted by the wet ball milling is ethanol (the mass ratio of solid matter to ethanol is 1.2), the ball-to-material ratio is 2,the time is 2h; drying the material obtained by wet ball milling at 80 ℃ for 5 hours to obtain a mixture;
(2) Transferring the mixture obtained in the step (1) to a muffle furnace, sintering for 7h at 350 ℃ in an air atmosphere, heating to 950 ℃ and sintering for 15h to obtain a target product, namely the layered oxide cathode material, wherein the theoretical chemical formula of the layered oxide cathode material is NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Example 8
A layered oxide cathode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Mixing Na 2 CO 3 、NiO、Fe 2 O 3 、Mn 2 O 3 Preliminary mixing was carried out at a molar ratio of 1.52; adding polystyrene with the mass of 2.5 percent based on 100 percent of the theoretical mass of the formed layered oxide, and mixing by wet ball milling; the organic solvent adopted by the wet ball milling is ethanol (the mass ratio of solid matter to ethanol is 1.2), the ball-to-material ratio is 1; drying the material obtained by wet ball milling for 5 hours at the temperature of 80 ℃ to obtain a mixture;
(2) Transferring the mixture obtained in the step (1) into a muffle furnace, sintering for 3h at 500 ℃ in an air atmosphere, heating to 950 ℃ and sintering for 15h to obtain a target product, namely the layered oxide anode material, wherein the theoretical chemical formula of the layered oxide anode material is NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Example 9
A layered oxide cathode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Mixing Na 2 CO 3 、NiO、Fe 2 O 3 、Mn 2 O 3 Preliminary mixing is carried out at a molar ratio of 1.545; adding 5% by mass of polydopamine into the formed layered oxide by taking the theoretical mass of the layered oxide as 100%, and mixing by wet ball milling; the organic solvent adopted by the wet ball milling is ethanol (the mass ratio of solid substances to ethanol is 1.2), the ball-to-material ratio is 1The speed is 200rpm, and the time is 3h; drying the material obtained by wet ball milling for 5 hours at the temperature of 80 ℃ to obtain a mixture;
(2) Transferring the mixture obtained in the step (1) to a muffle furnace, sintering for 5h at 450 ℃ in an air atmosphere, heating to 900 ℃ and sintering for 20h to obtain a target product, namely the layered oxide cathode material, wherein the theoretical chemical formula of the layered oxide cathode material is NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Example 10
A layered oxide cathode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Mixing Na 2 CO 3 、NiO、Fe 2 O 3 、Mn 2 O 3 Preliminary mixing is carried out at a molar ratio of 1.545; glucose was added thereto in an amount of 6% by mass based on 100% by mass of the formed layered oxide, and mixed by wet ball milling; the organic solvent adopted by the wet ball milling is ethanol (the mass ratio of solid matter to ethanol is 1.2), the ball-to-material ratio is 1; drying the material obtained by wet ball milling for 5 hours at the temperature of 80 ℃ to obtain a mixture;
(2) Transferring the mixture obtained in the step (1) into a muffle furnace, sintering for 5h at 450 ℃ in an air atmosphere, heating to 900 ℃ and sintering for 20h to obtain a target product, namely the layered oxide anode material, wherein the theoretical chemical formula of the layered oxide anode material is NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Comparative example 1
A layered oxide cathode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Mixing Na 2 CO 3 、NiO、Fe 2 O 3 、Mn 2 O 3 Performing wet ball milling at a molar ratio of 1.545; drying the material obtained by uniformly mixing the wet ball milling at 80 ℃ for 5 hours to obtain a mixture;
(2) And (2) transferring the mixture obtained in the step (1) to a muffle furnace, sintering for 5h at 450 ℃ in an air atmosphere, and then heating to 900 ℃ for sintering for 20h to obtain a target product, namely the layered oxide cathode material.
Comparative example 2
A layered oxide cathode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Mixing Na 2 CO 3 、NiO、Fe 2 O 3 、Mn 2 O 3 Performing wet ball milling at a molar ratio of 1.545; drying the material obtained by uniformly mixing the wet ball milling at 80 ℃ for 5 hours to obtain a mixture;
(2) Transferring the mixture obtained in the step (1) into a muffle furnace, sintering for 5h at 450 ℃ in an air atmosphere, and then heating to 900 ℃ to sinter for 20h to obtain a layered oxide;
(3) And (3) uniformly mixing the layered oxide obtained in the step (2) with polystyrene with the mass of 4% by taking the mass of the layered oxide as 100%, then placing the mixture into a muffle furnace, and sintering the mixture for 5 hours at 800 ℃ in an air atmosphere to obtain the layered oxide cathode material.
Comparative example 3
A layered oxide cathode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Na is mixed with 2 CO 3 、NiO、Fe 2 O 3 、Mn 2 O 3 Performing wet ball milling at a molar ratio of 1.545; drying the material obtained by uniformly mixing the wet ball milling at 80 ℃ for 5 hours to obtain a mixture;
(2) Transferring the mixture obtained in the step (1) to a muffle furnace, sintering for 5h at 450 ℃ in an air atmosphere, and then heating to 900 ℃ for sintering for 20h to obtain a layered oxide;
(3) And (3) uniformly mixing the layered oxide obtained in the step (2) with polystyrene with the mass of 4% by taking the mass of the layered oxide as 100%, then placing the mixture in a muffle furnace, and sintering the mixture for 5 hours at 800 ℃ in a nitrogen atmosphere to obtain the layered oxide cathode material.
Comparative example 4
A layered oxide cathode material and a preparation method thereof are disclosed, wherein the preparation method comprises the following steps:
(1) Mixing Na 2 CO 3 、NiO、Fe 2 O 3 、Mn 2 O 3 Performing wet ball milling at a molar ratio of 1.545; drying the material obtained by uniformly mixing the wet ball milling at 80 ℃ for 5 hours to obtain a mixture;
(2) Transferring the mixture obtained in the step (1) to a muffle furnace, sintering for 5h at 450 ℃ in an air atmosphere, and then heating to 900 ℃ for sintering for 20h to obtain a layered oxide;
(3) Adding 3g of trimethylaluminum (2.0M toluene solution from Michalin) into 150mL of toluene, stirring uniformly, adding 150g of the layered oxide obtained in step (2) into the solution, heating to 30 ℃, continuously stirring for 12h, centrifuging the obtained product, washing with toluene to remove unreacted trimethylaluminum, separating the product again, and vacuum sintering at 200 ℃ for 3h to obtain Al 2 O 3 And the coated layered oxide is the layered oxide cathode material.
The performance of the layered oxide cathode materials provided in examples 1 to 10 and comparative examples 1 to 4 was tested by the following specific method:
1. testing of crystal structure
An X-ray diffractometer (XRD, shimadzu, XRD 6100) is used to test the crystal structure of the layered oxide positive electrode material, wherein, the XRD pattern of the layered oxide positive electrode material provided in example 1 is shown in fig. 1, and it can be seen from fig. 1 that the layered oxide positive electrode material has good crystallinity and no impurity peak.
2. Elemental analysis
The method for preparing the sample comprises the following steps of (1) performing elemental analysis on the layered oxide cathode material by using an inductively coupled plasma emission spectrometer (ICP, agilent 5100): putting 1.0g of a sample to be detected in a 50mL PTFE beaker, adding 3mL of concentrated nitric acid and 9mL of hydrochloric acid, heating on a hot plate at 260 ℃ for 30min, filtering, transferring to a 100mL volumetric flask, and fixing the volume to be detected; the ICP test was performed on the test solutions, and the results are shown in table 1:
TABLE 1
3. Electrochemical Performance test
Assembling the sodium-ion button cell by adopting the layered oxide anode material to be tested: mixing a layered oxide positive electrode material, conductive carbon black (Super P) and polyvinylidene fluoride (PVDF) according to a mass ratio of 8; assembling the prepared positive pole piece and a sodium metal pole piece into a sodium ion button cell, dissolving sodium perchlorate with the concentration of 1M in Propylene Carbonate (PC)/fluoroethylene carbonate (FEC) (mass ratio 97, shenzhen friend research), and obtaining electrolyte; after the electricity-buckling assembly is completed, the capacity, circulation and other tests are carried out on the blue battery test system according to the following steps: standing for 2h; constant current charging and discharging, wherein the charging and discharging voltage interval is 2.0-4.3V, the cycle multiplying power is 0.5C and 2.0C respectively, and the rated gram capacity is 120mAh/g.
The test results are shown in table 2:
TABLE 2
The performance test data in table 2 show that, compared with the layered oxide cathode material prepared by the conventional solid phase method (comparative example 1), the carbon-containing material is introduced into the preparation method provided by the invention, and the layered oxide cathode material obtained by the design of the raw materials and the coordination and synergistic effect of the specific process method has significantly improved structural stability and electrochemical performance, and as the cathode active material, the specific capacities of the cathode active material under 0.1C, 0.5C, 1.0C, 2.0C and 5.0C are 122.8-124.1mAh/g, 118.5-120.9mAh/g, 109.3-115.0mAh/g, 92.4-101.3mAh/g and 79.5-84.1mAh/g respectively, the capacity retention rate of the cathode active material after 100 cycles of 0.5C is 82.1-88.4%, the retention rate of the capacity of the cathode active material after 300 cycles of 2.0C is 60.1-68.6%, and particularly the cathode active material has excellent cycle performance under high rate, and the cathode active material has obvious breakthrough in terms of structural stability and structural integrity.
In the preparation method provided by the invention, a series of carbonization and oxidation reactions are carried out on the carbonaceous material with a specific dosage in the sintering process, so that the oxygen distribution condition of the surface of the layered oxide is regulated and controlled, an oxygen-poor stable phase is formed, an oxygen-poor coating layer which has the same components as the bulk material, is tightly combined and has a stable structure is generated in situ, and the obtained layered oxide positive electrode material has a structure gradually transited from inside to outside and shows excellent structural integrity, stability and electrochemical performance. If the preparation method defined by the invention is not adopted, the carbonization/oxidation reaction of the carbonaceous material cannot regulate the formation of the layered oxide and the surface oxygen distribution, a specific oxygen-deficient structure cannot be formed, and the electrochemical performance of the cathode material is poor (comparative example 2); in addition, the carbon-containing material in the comparative example 3 forms the carbon coating layer in the sintering process, so that the conductivity of the material can be improved to a certain extent, the specific capacity is improved, but the uniform oxygen-deficient coating layer cannot be formed, and the cycle performance is not obviously improved; comparative example 4 formation of Al on layered oxide 2 O 3 Compared with the layered oxide which is not coated, the coating layer has improved cycle performance, but because the coating layer and the layered oxide body have different components, an interface problem exists, so that the capacity retention rate after multi-circle circulation under high multiplying power is lower, and the improvement effect of the cycle performance is poor.
The applicant states that the present invention is illustrated by the above examples to the layered oxide cathode material of the present invention and the preparation method and application thereof, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modifications to the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific forms, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The preparation method of the layered oxide anode material is characterized in that the layered oxide anode material is NaxMO 2 Wherein x is more than 0 and less than or equal to 1, M is selected from any one or the combination of at least two of Ni, co, mn, fe, cu, ti and Sn;
the preparation method comprises the following steps: mixing a sodium source, an M metal source and a carbonaceous material to obtain a mixture; and sintering the mixture under an aerobic condition to obtain the layered oxide cathode material.
2. The method of claim 1, wherein the sodium source comprises sodium hydroxide and/or sodium salt;
preferably, the sodium source comprises any one of sodium hydroxide, sodium carbonate, sodium acetate, sodium sulfate, sodium nitrate, sodium chloride or a combination of at least two of the foregoing;
preferably, the M metal source comprises a nickel source and a manganese source, and at least one of an iron source, a cobalt source, a copper source, a titanium source, and a tin source, further preferably, the M metal source comprises a combination of a nickel source, a manganese source, and an iron source;
preferably, the nickel source comprises any one of nickel oxide, nickel hydroxide, nickel salt or a combination of at least two thereof;
preferably, the manganese source comprises an oxide and/or salt of manganese;
preferably, the iron source comprises any one of iron oxide, iron salt, ferrous salt or a combination of at least two thereof.
3. The method according to claim 1 or 2, wherein the carbonaceous material comprises any one of or a combination of at least two of a carbohydrate, polystyrene, polydopamine;
preferably, the saccharide compound comprises any one of glucose, sucrose, chitosan, maltose and starch or a combination of at least two of the above;
preferably, the carbonaceous material has a mass of 0.2 to 5.5%, more preferably 1 to 5%, based on 100% by mass of the layered oxide made of the sodium source and the M metal source.
4. A method of preparation according to any one of claims 1 to 3, characterized in that the method of mixing is ball milling, preferably wet ball milling;
preferably, the ball milling is carried out in the presence of an organic solvent comprising an alcoholic solvent and/or a ketone solvent;
preferably, the ball-milling has a ball-to-material ratio of (0.5-2): 1;
preferably, the rotation speed of the ball mill is 100-350rpm;
preferably, the ball milling time is 1-5h;
preferably, the method also comprises a drying step after the ball milling is finished;
preferably, the temperature of the drying is 60-100 ℃;
preferably, the drying time is 1-6h.
5. The production method according to any one of claims 1 to 4, wherein the sintering comprises a first stage sintering and a second stage sintering which are performed in this order, and the temperature of the first stage sintering is less than that of the second stage sintering;
preferably, the temperature of the first stage sintering is 300-600 ℃;
preferably, the time of the first sintering stage is 2-7h;
preferably, the temperature of the second-stage sintering is 800-950 ℃;
preferably, the time for the second stage sintering is 10-30h.
6. The production method according to any one of claims 1 to 5, characterized by comprising the steps of:
(1) Mixing a sodium source, an M metal source and a carbon-containing material through wet ball milling, and drying after uniform mixing to obtain a mixture;
the M metal source comprises a nickel source, a manganese source and any one of an iron source, a cobalt source, a copper source, a titanium source and a tin source; the carbon-containing material comprises any one or a combination of at least two of carbohydrate, polystyrene and polydopamine; the mass of the carbon-containing material is 0.2-5.5% by taking the mass of the layered oxide prepared from the sodium source and the M metal source as 100%;
the ball-material ratio of the wet ball milling is (0.5-2) to 1, the rotating speed is 100-350rpm, and the time is 1-5h;
(2) Sequentially carrying out first-stage sintering and second-stage sintering on the mixture obtained in the step (1) under an aerobic condition to obtain the layered oxide anode material;
wherein the temperature of the first-stage sintering is 300-600 ℃, and the time is 2-7h; the temperature of the second-stage sintering is 800-950 ℃, and the time is 10-30h.
7. A layered oxide positive electrode material, characterized in that it is produced by the production method according to any one of claims 1 to 6.
8. The layered oxide cathode material according to claim 7, wherein the layered oxide cathode material is NaxMO 2 (ii) a Wherein x is 0.5-1, M is selected from any one or the combination of at least two of Ni, co, mn, fe, cu, ti and Sn;
preferably, the layered oxide cathode material is NaxNiyMnzM' (1-y-z) O 2 (ii) a Wherein y is more than 0 and less than 1, z is more than 0 and less than 1, M' is selected from any one or the combination of at least two of Co, fe, cu, ti and Sn;
preferably, the layered oxide isThe pole material is NaxNiyMnzFe (1-y-z) O 2 。
9. Use of a layered oxide positive electrode material according to claim 7 or 8 in an electrochemical device;
preferably, the electrochemical device comprises a sodium ion battery or a capacitor.
10. A sodium-ion battery, characterized in that it comprises a layered oxide positive electrode material according to claim 7 or 8.
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