CN115676915B - 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
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- CN115676915B CN115676915B CN202211351217.8A CN202211351217A CN115676915B CN 115676915 B CN115676915 B CN 115676915B CN 202211351217 A CN202211351217 A CN 202211351217A CN 115676915 B CN115676915 B CN 115676915B
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- layered oxide
- sodium
- positive electrode
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 238000005245 sintering Methods 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 55
- 239000011734 sodium Substances 0.000 claims abstract description 54
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 238000002156 mixing Methods 0.000 claims abstract description 43
- 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 37
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 37
- 239000010406 cathode material Substances 0.000 claims abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- 239000001301 oxygen Substances 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 59
- 239000000463 material Substances 0.000 claims description 51
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 43
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- 238000000576 coating method Methods 0.000 claims description 14
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 13
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
Classifications
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- 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
Abstract
The invention provides a layered oxide positive electrode material, a preparation method and application thereof, wherein the layered oxide positive electrode material is NaxMO 2 X is more than 0 and less than or equal to 1, and M is selected from any one or a combination of at least two of Ni, co, mn, fe, cu, ti, 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 the aerobic condition to obtain the layered oxide cathode material. According to the invention, through the design and synergistic effect of the raw materials and the process method, the oxygen distribution on the surface of the layered oxide is regulated and controlled to form an oxygen-deficient stable phase, and the obtained layered oxide anode material has a structure gradually transiting from inside to outside, has excellent structural integrity, stability and electrochemical performance, and can effectively improve the multiplying power performance and the cycle performance of a battery. The preparation method has the advantages of simple process route, easy realization of large-scale production and 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 positive electrode material, a preparation method and application thereof.
Background
Along with the development and progress of energy technology, lithium batteries are widely applied to the fields of energy storage, electric automobiles, consumer electronic products and the like, and become an indispensable component of life of people at present. However, due to the limitation of the reserves of common resources of lithium batteries such as lithium, nickel and the like, the price of raw materials of the lithium batteries is continuously increased in recent years, the cost performance of the lithium batteries is seriously reduced, and the application of the lithium batteries is influenced. In addition, the safety of lithium batteries is a non-negligible problem due to the continuous pursuit of energy density of lithium batteries.
Sodium batteries are an important branch in energy technology, compared with lithium batteries, the storage quantity of sodium is far higher than that of lithium, and along with the continuous maturity of technologies such as seawater sodium extraction and the like, the price of sodium also continues to be low, which is also an inherent advantage of the price of sodium batteries. Moreover, the lithium battery is easy to generate dendrites and the like, so that potential safety hazards of spontaneous combustion of a short circuit are caused, and the sodium battery is difficult to generate dendrites, so that the safety is far higher than that of the lithium battery. Considering comprehensively, 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 special advantages, and the sodium battery has great potential to fill the market blank between the lithium battery and the lead-acid battery. Currently, commercial negative electrode materials of sodium batteries mainly comprise hard carbon, and positive electrode materials mainly comprise Prussian, polyanion, oxide and the like; among them, oxide positive electrode materials have been attracting attention in industry, and have high theoretical capacity, simple structure, and easy synthesis.
Transition metal layered oxides are a representative class of oxide-based cathode materials, with nickel-manganese-based layered oxides being of greater interest. Similar to the high nickel oxide positive electrode material in the lithium battery, the gram capacity of the layered oxide has a direct relation with the Ni content therein, and the specific capacity of the oxide positive electrode material can be effectively improved by improving the Ni content. However, during cycling, too high Ni content directly affects the structural stability of the layered oxide. Due to Ni 4+ The catalyst has higher activity in electrolyte, and when the Ni content is higher than 60%, the cycle 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 will further accelerate the decay of the material properties.
In order to improve the performance defect of nickel-manganese-based layered oxide, attempts are made to construct a coating layer on the surface of a layered oxide material, and the electrolyte and the layered structure oxide can be separated to avoid direct connectionAnd the contact reduces the occurrence of side reaction, and plays roles in inhibiting phase change and improving the structural stability of the material. For example, CN113889613a discloses a layered sodium-ion battery positive electrode material with a gradient structure, and the preparation method comprises the following steps: uniformly mixing a layered oxide positive electrode material with a P2 phase structure with a magnesium source, and enabling Mg to react by a low-temperature molten salt reaction method 2+ Into the layered oxide to form a coating with MgO and gradient Mg 2+ Doped layered oxide positive electrode material; na in Mg-rich layered oxide formed by the surface layer in the low temperature molten salt process + 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 the bulk phase structure of a P2 type layered oxide and are uniformly enriched on the surface of particles in the form of zinc oxide, thereby improving the electrochemical performance of the P2 type nickel-manganese-based layered oxide positive electrode material. CN109638273a discloses a coating method of a positive electrode material of a sodium ion battery, firstly, uniformly mixing a layered oxide positive electrode material, a coating precursor and a solvent, then spray drying to obtain a positive electrode material coated by the coating precursor, and then secondary sintering the materials to form an oxide shell, thereby obtaining the layered oxide positive electrode material coated by the oxide; wherein the coating precursor is one or more of Al, mg, ti, zn, zr, nb or La oxide, nitrate and hydrate thereof, sulfate and hydrate thereof and organic salt.
In general, in the current layered oxide cathode materials, materials commonly used as coating layers include metal oxides such as aluminum oxide, magnesium oxide, titanium oxide, zinc oxide, and the like, and common coating methods include a chemical method, a ball milling method, an atomic layer deposition technique, and the like. Because the sodium-electricity anode material has higher sensitivity to moisture, the application of the coating method is limited, and the coating is usually completed by multiple times of sintering, so that higher preparation difficulty and processing cost are brought. Furthermore, 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 of the coating layer and the cathode material, affecting the ionic conductivity of the material. In addition, due to different material structures, it is difficult to ensure that the expansion coefficient of the coating layer and that of the layered oxide cathode material are kept the same in the charge and discharge process, so that the coating layer is damaged or falls off, and the performance of the sodium battery is further affected.
Therefore, there is a need in the art to develop sodium-electricity positive electrode materials that have more excellent electrochemical properties, and in particular, better stability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a layered oxide positive electrode material, a preparation method and application thereof, and the design of raw materials, particularly carbon-containing materials and the interaction of the raw materials and a specific process enable the surface of the obtained layered oxide positive electrode material to form an oxygen-deficient structure, so that in-situ modification and coating of the layered oxide are realized. The layered oxide cathode material has excellent electrochemical performance, structural integrity and stability, so that the rate performance and the cycle performance of the sodium ion battery are improved.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a layered oxide cathode material, where the layered oxide cathode material is NaxMO 2 Wherein x is more than 0 and less than or equal to 1, and M is selected from any one or a combination of at least two of Ni, co, mn, fe, cu, ti, 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 the aerobic condition to obtain the layered oxide cathode material.
In the preparation method of the layered oxide cathode material, a carbon-containing material is introduced in a mixing stage of a sodium source and an M metal source to obtain a mixture of a precursor (the sodium source and the M metal source) and a composite structure of the carbon-containing material. In the sintering process of the mixture, a series of carbonization and oxidation reactions are carried out on the carbonaceous material, oxygen is taken away from the surface of the precursor in a short time, so that oxygen in the structure is quickly lost, the surface oxygen of the layered oxide prepared from a sodium source and an M metal source is quickly lost, the layered oxide is subjected to phase transition from a layered structure to a rock salt phase, the transition from the layered oxide to the rock salt phase is gradually realized from inside to outside, the surface of the obtained layered oxide anode material is provided with a stable oxygen-deficient structure, namely an oxygen-deficient coating layer is formed, and the coating layer is synchronously formed in the process of forming the layered oxide by the sodium source and the M metal source, so that the layered oxide anode material has the characteristic of in-situ modification/coating; more importantly, the coating layer and the bulk material (bulk phase) of the layered oxide have the same components, the structure gradually transits from inside to outside, the coating layer is tightly combined with the bulk material (bulk phase) of the layered oxide, and the generation of an interface is reduced. Meanwhile, as the rock salt phase generated in situ is of an oxygen-deficient structure, the 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, during 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 a target product.
In the invention, the design of raw materials, in particular the introduction of carbonaceous materials, is matched with a specific process method, and the oxygen distribution condition of the surface of the layered oxide is regulated and controlled to form an oxygen-deficient stable phase, so that a coating layer which is the same as the components of the bulk material, tightly combined and stable in structure is generated in situ, the obtained layered oxide anode material has a structure which gradually transits from inside to outside, the interface problem and the coating layer breakage and shedding problem caused by conventional coating are avoided, and the layered oxide anode material has excellent structural integrity, stability and electrochemical performance. The preparation method has the advantages of wide sources of raw materials, 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 or a combination of at least two of sodium hydroxide, sodium carbonate, sodium acetate, sodium sulfate, sodium nitrate, sodium chloride.
In the invention, M in the M metal sourceNamely NaxMO 2 M of Ni, co, mn, fe, cu, ti, sn, any one or a combination of at least two; the M metal source is selected from any one or a combination of at least two of a nickel source, a manganese source, an iron source, a cobalt source, a copper source, a titanium source and a tin source.
Preferably, the M metal source includes 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 cathode 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 Any one or a combination of at least two of the nickel salts.
Preferably, the nickel salt comprises any one or a combination of at least two of nickel nitrate, nickel sulfate, nickel carbonate and nickel acetate; the nickel salt optionally contains bound water.
Preferably, the manganese source comprises manganese oxide and/or manganese salt.
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 these.
Preferably, the manganese salt comprises any one or a combination of at least two of manganese carbonate, manganese sulfate, manganese chloride and manganese nitrate; the manganese salt optionally contains bound water.
Preferably, the iron source comprises any one or a combination of at least two of iron oxide, iron salt (ferric salt), ferrous salt (ferrous salt).
Preferably, the iron oxide comprises FeO, fe 2 O 3 、Fe 3 O 4 Any one or a combination of at least two of these.
Preferably, the iron salt comprises any one or a combination of at least two of ferric nitrate, ferric phosphate, and ferric carbonate.
Preferably, the ferrous salt comprises any one or a combination of at least two of ferrous sulfate, ferrous oxalate, ferrous phosphate, ferrous nitrate, ferrous carbonate.
In the invention, the respective dosage of the sodium source and the M metal source is calculated as the target product NaxMO 2 The stoichiometric ratio of Na to M was determined.
Preferably, the sodium source may be added in excess relative to the M metal source.
Preferably, the actual amount of sodium source is 101-113%, for example 102%, 103%, 104%, 105%, 107%, 109%, 110% or 112%, and specific point values between the above point values, calculated as 100% of the theoretically required sodium source, is not exhaustive of the specific point values included in the range, for reasons of length and for reasons of simplicity, and is more preferably 101-105%.
Preferably, the carbonaceous material comprises any one or a combination of at least two of a saccharide compound, polystyrene, polydopamine.
Preferably, the saccharide compound comprises any one or a combination of at least two of glucose, sucrose, chitosan, maltose and starch.
Preferably, the carbonaceous material has a mass of 0.2 to 5.5%, for example, may be 0.3%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%, and specific point values between the above point values, calculated on the basis of 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 the present invention is not exhaustive of the specific point values included in the range, more preferably 1 to 5%, for reasons of brevity.
According to the preferable technical scheme, the theoretical mass of the layered oxide obtained by calculation according to the dosages of the sodium source and the M metal source is 0.2-5.5%, more preferably 1-5% of the theoretical mass of the layered oxide, so that the carbonaceous material is subjected to a series of carbonization and oxidation reactions in the subsequent sintering process, and an oxygen distribution on the surface of the layered oxide material is effectively regulated, and an oxygen-deficient stable phase is formed on the surface, so that a coating layer which is identical to the component of the layered oxide body (bulk), different in structure, tightly combined and stable in structure is formed in situ, and the layered oxide positive electrode material has excellent structural integrity, stability and electrochemical performance. If the quality of the carbonaceous 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 positive electrode material is affected, excessive sodium carbonate is formed on the surface, and the processing performance of the positive electrode material is directly affected by excessive residual alkali.
Preferably, in the mixing, the sodium source and the M metal source are initially mixed, and then the carbonaceous material is added for mixing.
Preferably, the method of mixing is ball milling, more preferably wet ball milling.
Preferably, the ball milling is carried out in the presence of an organic solvent (wet ball milling), including an alcoholic solvent and/or a ketone solvent.
Preferably, the alcohol solvent comprises any one or a combination of at least two of methanol, ethanol, n-propanol and isopropanol, and further preferably ethanol.
Preferably, the ketone solvent comprises acetone and/or methyl ethyl ketone, further preferably acetone.
Preferably, the ball-to-material ratio of the ball mill is (0.5-2): 1, which may be, for example, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, or 1.9:1, etc.
Preferably, the ball milling is performed at a rotational speed of 100-350rpm, for example, 120rpm, 150rpm, 180rpm, 200rpm, 220rpm, 250rpm, 280rpm, 300rpm, 320rpm or 340rpm, and specific point values between the above point values, are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the ball milling time is 1-5h, for example, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h or 4.5h, and specific point values between the above point values, are limited in length and for brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the ball milling further comprises a drying step after completion of the ball milling.
Preferably, the drying temperature is 60-100deg.C, such as 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ or 95 ℃, and specific point values between the above point values, although the invention is not exhaustive of the specific point values included in the range for reasons of space and for reasons of simplicity.
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 point values between the above point values, are limited in length and for brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the sintering is performed in an air atmosphere.
In the present invention, the sintering is performed in any device known in the art in which sintering can occur, preferably the device for sintering comprises a muffle, 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 sequentially performed, wherein the temperature of the first-stage sintering is less than the temperature of the second-stage sintering.
Preferably, the temperature of the first stage sintering is 300-600 ℃, and may be 320 ℃, 350 ℃, 380 ℃, 400 ℃, 420 ℃, 450 ℃, 480 ℃, 500 ℃, 520 ℃, 550 ℃ or 580 ℃ and specific point values between the above point values, for example, and the present invention is not exhaustive of the specific point values included in the range for the sake of brevity and conciseness.
Preferably, the time of the first stage sintering is 2-7h, for example, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h or 6.5h, and specific point values among the above point values, are limited in length and for brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the second stage sintering temperature is 800-950 ℃, such as 810 ℃, 830 ℃, 850 ℃, 870 ℃, 890 ℃, 900 ℃, 920 ℃, or 940 ℃, and specific point values between the above point values, which are limited in space and for simplicity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the second stage sintering is performed for a period of time ranging from 10 to 30 hours, for example, 11 hours, 13 hours, 15 hours, 17 hours, 19 hours, 20 hours, 21 hours, 23 hours, 25 hours, 27 hours or 29 hours, and specific point values between the above point values, which are limited in space and for the sake of brevity, the present invention is not exhaustive.
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 uniformly 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 carbonaceous material comprises any one or a combination of at least two of saccharide compounds, polystyrene and polydopamine; the mass of the carbonaceous material is 0.2-5.5% based on the mass of the layered oxide made of the sodium source and the M metal source being 100%;
the ball-material ratio of the wet ball milling is (0.5-2) 1, the rotating speed is 100-350rpm, and the time is 1-5h;
(2) Sequentially performing first-stage sintering and second-stage sintering on the mixture obtained in the step (1) under the 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 cathode material prepared by the preparation method as described in the first aspect.
The layered oxide positive electrode material is NaxMO 2 Wherein M is selected from any one or a combination of at least two of Ni, co, mn, fe, cu, ti, 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 point values between the above point values, are limited in space and for brevity, the present invention is not exhaustive of the specific point values included in the ranges.
Preferably, x is 0.5 to 1, preferably 0.5 < x.ltoreq.1, and more preferably 0.6 < x.ltoreq.1.
Preferably, the layered oxide positive electrode material is NaxNiyMnzM' (1-y-z) O 2 The method comprises the steps of carrying out a first treatment on the surface of the M' is selected from any one or a combination of at least two of Co, fe, cu, ti, sn; therefore, the layered oxide positive electrode material is a nickel-manganese-based layered oxide positive electrode material.
Where 0 < y < 1, y 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 or 0.9, and specific point values between the above point values, are limited in space and for brevity, the invention is not exhaustive of the specific point values included in the ranges, more preferably 0 < y.ltoreq.0.5.
0 < z < 1, z 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 or 0.9, and specific point values between the above point values, are limited in scope and for brevity, the invention is not exhaustive of the specific point values included in the ranges, more preferably 0 < z.ltoreq.0.5.
0＜y+z≤1。
Preferably, the layered oxide positive electrode material is NaxNiyMnzFe (1-y-z) O 2 。
According to the preparation method, through the optimal design of the preparation method, the surface oxygen distribution of the layered oxide is effectively regulated and controlled, the layered structure within the thickness of about 10nm on the surface is modified, and an oxygen-deficient stable phase is formed on the surface of the material, namely a homogeneous oxygen-deficient coating layer is formed; 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 problem is avoided; and the coating layer has stable structure, can not be damaged or fall off, and can provide continuous protection for the layered oxide. The layered oxide positive electrode material has a structure gradually transiting from inside to outside and has excellent structural integrityAnd stability, excellent in ion conductivity, capacity, excellent in electrochemical performance; layered oxide positive electrode material NaxMO 2 Preferably 0.65-1 (x is about 0.67-0.7 of the P2 phase and x is about 0.7-1 of the O3 phase), the higher sodium content being capable of providing sufficient Na + To perform electrochemical reactions, so that the sodium ion battery comprising the same has excellent capacity and cycle performance.
Preferably, the specific capacity of the layered oxide positive electrode 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 positive electrode 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 positive electrode 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 positive electrode 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 positive electrode material at 5.0 ℃ 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 the use of a layered oxide cathode material as described in 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 cathode material as described in 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 carbonaceous material and the cooperation and synergy of the carbonaceous material and 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 is the same as the component of a bulk material, different in structure, tightly combined and stable in structure is generated in situ. The preparation method has the advantages of wide sources of raw materials, simple process route, easy realization of large-scale production and wide application prospect.
(2) The layered oxide positive electrode material has excellent stability, specific capacity and rate capability, is used for a sodium ion battery, can effectively improve the rate capability and cycle capability of the sodium ion battery, has a capacity retention rate of more than or equal to 82.1% in 100 cycles of 0.5C and a capacity retention rate of more than or equal to 60% in 300 cycles of 2.0C, and has excellent cycle capability especially under high rate.
Drawings
Fig. 1 is an XRD pattern of the layered oxide cathode material provided in example 1.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The terms "comprising," "including," "having," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, step, 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, step, method, article, or apparatus.
"optionally" or "any" means that the subsequently described event or event may or may not occur, and that the description includes both cases where the event occurs and cases where the event does not occur.
The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise.
The description of the terms "one embodiment," "some embodiments," "exemplarily," "specific examples," or "some examples," etc., herein described means that a specific 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, the schematic representations of the above terms are not necessarily for the same embodiment or example.
The technical features of the respective embodiments of the present invention may be combined with each other as long as they do not collide with each other.
The raw materials involved in the following specific embodiments of the invention are all commercial products; wherein, polystyrene (PS) is purchased from microphone (L815936, polystyrene microsphere, 0.05-0.1 μm); polydopamine was purchased from Siam Azithrone Yue Shengwu under the designation Q-0094192.
Example 1
A layered oxide positive electrode material and a preparation method thereof are provided, 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 performed at a molar ratio of 1.545:1:0.5:0.5 (Na 2 CO 3 3% excess); adding polystyrene with the mass of 1% into the layered oxide with the theoretical mass of the formed layered oxide of 100%, and mixing by wet ball milling; the organic solvent adopted by the wet ball milling is ethanol (the mass ratio of solid matters to ethanol is 1:1.2), the ball-material ratio is 1:1, the rotating speed is 200rpm, and the time is 3 hours; 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 5 hours at 450 ℃ in an air atmosphere, and then heating to 900 ℃ and sintering for 20 hours to obtain a target product, namely the layered oxide positive electrode material, wherein the theoretical chemical formula of the layered oxide positive electrode material is NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Example 2
A layered oxide positive electrode material and a preparation method thereof are provided, 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 performed at a molar ratio of 1.545:1:0.5:0.5; adding polystyrene with the mass of 2% into the layered oxide with the theoretical mass of the formed layered oxide of 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 1:1.2), the ball-material ratio is 1:1, the rotating speed is 200rpm, and the time is 3 hours; drying the material obtained by wet ball milling at 70 ℃ for 5 hours to obtain a mixture;
(2) Transferring the mixture obtained in the step (1) into a muffle furnace, sintering for 5 hours at 450 ℃ in an air atmosphere, and then heating to 900 ℃ and sintering for 20 hours to obtain a target product, namely the layered oxide positive electrode material, wherein the theoretical chemical formula of the layered oxide positive electrode material is NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Example 3
A layered oxide positive electrode material and a preparation method thereof are provided, 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 performed at a molar ratio of 1.545:1:0.5:0.5; adding polystyrene with the mass of 3% into the layered oxide with the theoretical mass of the formed layered oxide of 100%, and mixing by wet ball milling; the organic solvent adopted by the wet ball milling is ethanol (the mass ratio of solid matters to ethanol is 1:1.2), the ball-material ratio is 1:1, the rotating speed is 200rpm, and the time is 3 hours; 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 5 hours at 450 ℃ in an air atmosphere, and then heating to 900 ℃ and sintering for 20 hours to obtain a target product, namely the layered oxide positive electrode material, wherein the theoretical chemical formula of the layered oxide positive electrode material is NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Example 4
A layered oxide positive electrode material and a preparation method thereof are provided, 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 performed at a molar ratio of 1.545:1:0.5:0.5; adding 4% polystyrene by mass based on 100% 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 matters to ethanol is 1:1.2), the ball-material ratio is 1:1, the rotating speed is 200rpm, and the time is 3 hours; 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 5 hours at 450 ℃ in an air atmosphere, and then heating to 900 ℃ and sintering for 20 hours to obtain a target product, namely the layered oxide positive electrode material, wherein the theoretical chemical formula of the layered oxide positive electrode material is NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Example 5
A layered oxide positive electrode material and a preparation method thereof are provided, 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 performed at a molar ratio of 1.545:1:0.5:0.5; adding polystyrene with the mass of 5% into the layered oxide with the theoretical mass of the formed layered oxide of 100%, and mixing by wet ball milling; the organic solvent adopted by the wet ball milling is ethanol (the mass ratio of solid matters to ethanol is 1:1.2), the ball-material ratio is 1:1, the rotating speed is 200rpm, and the time is 3 hours; 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 5 hours at 450 ℃ in an air atmosphere, and then heating to 900 ℃ and sintering for 20 hours to obtain a target product, namely the layered oxide positive electrode material, wherein the theoretical chemical formula of the layered oxide positive electrode material is NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Example 6
A layered oxide positive electrode material and a preparation method thereof are provided, 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 performed at a molar ratio of 1.545:1:0.5:0.5; adding 6% polystyrene by mass based on 100% 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 matters to ethanol is 1:1.2), the ball-material ratio is 1:1, the rotating speed is 200rpm, and the time is 3 hours; 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 5 hours at 450 ℃ in an air atmosphere, and then heating to 900 ℃ and sintering for 20 hours to obtain a target product, namely the layered oxide positive electrode material, wherein the theoretical chemical formula of the layered oxide positive electrode material is NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Example 7
A layered oxide positive electrode material and a preparation method thereof are provided, 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 performed at a molar ratio of 1.55:1:0.5:0.5; adding 4.5% polystyrene by mass based on 100% 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 matters to ethanol is 1:1.2), the ball-material ratio is 2:1, the rotating speed is 300rpm, and the time is 2 hours; 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 7h at 350 ℃ in air, and then heating to 950 ℃ and sintering for 15h to obtain a target product, namely the layered oxide positive electrode material, wherein the theoretical chemical formula of the layered oxide positive electrode material is NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Example 8
A layered oxide positive electrode material and a preparation method thereof are provided, 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 performed at a molar ratio of 1.52:1:0.5:0.5; adding 2.5% polystyrene by mass based on 100% 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 matters to ethanol is 1:1.2), the ball-material ratio is 1:1, the rotating speed is 150rpm, and the time is 5 hours; 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 3 hours at 500 ℃ in an air atmosphere, and then heating to 950 ℃ and sintering for 15 hours to obtain a target product, namely the layered oxide positive electrode material, wherein the theoretical chemical formula of the layered oxide positive electrode material is NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Example 9
A layered oxide positive electrode material and a preparation method thereof are provided, 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 performed at a molar ratio of 1.545:1:0.5:0.5; adding 5% polydopamine by mass based on 100% of 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 matters to ethanol is 1:1.2), the ball-material ratio is 1:1, the rotating speed is 200rpm, and the time is 3 hours; 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 5 hours at 450 ℃ in an air atmosphere, and then heating to 900 ℃ and sintering for 20 hours to obtain a target product, namely the layered oxide positive electrode material, wherein the theoretical chemical formula of the layered oxide positive electrode material is NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Example 10
A layered oxide positive electrode material and a preparation method thereof are provided, 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 performed at a molar ratio of 1.545:1:0.5:0.5; adding glucose with the mass of 6% into the formed layered oxide with the theoretical mass of 100%, and mixing by wet ball milling; the organic solvent adopted by the wet ball milling is ethanol (the mass ratio of solid matters to ethanol is 1:1.2), the ball-material ratio is 1:1, the rotating speed is 200rpm, and the time is 3 hours; 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 5 hours at 450 ℃ in an air atmosphere, and then heating to 900 ℃ and sintering for 20 hours to obtain a target product, namely the layered oxide positive electrode material, wherein the theoretical chemical formula of the layered oxide positive electrode material is NaNi 1/3 Fe 1/ 3 Mn 1/3 O 2 。
Comparative example 1
A layered oxide positive electrode material and a preparation method thereof are provided, 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 Carrying out wet ball milling according to a molar ratio of 1.545:1:0.5:0.5, wherein an organic solvent adopted by the wet ball milling is ethanol (the mass ratio of solid matters to ethanol is 1:1.2), the ball-material ratio is 1:1, the rotating speed is 200rpm, and the time is 3 hours; 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 5 hours at 450 ℃ in air, and then heating to 900 ℃ and sintering for 20 hours to obtain a target product, namely the layered oxide cathode material.
Comparative example 2
A layered oxide positive electrode material and a preparation method thereof are provided, 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 At a molar ratio of 1.545:1:0.5:0.5Performing wet ball milling by using ethanol as an organic solvent (the mass ratio of solid matters to ethanol is 1:1.2), wherein the ball-material ratio is 1:1, the rotating speed is 200rpm, and the time is 3 hours; 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 5 hours at 450 ℃ in air, and then heating to 900 ℃ for sintering for 20 hours 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% based on the mass of the layered oxide of 100%, then placing the mixture in a muffle furnace, and sintering the mixture at 800 ℃ for 5 hours in an air atmosphere to obtain the layered oxide anode material.
Comparative example 3
A layered oxide positive electrode material and a preparation method thereof are provided, 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 Carrying out wet ball milling according to a molar ratio of 1.545:1:0.5:0.5, wherein an organic solvent adopted by the wet ball milling is ethanol (the mass ratio of solid matters to ethanol is 1:1.2), the ball-material ratio is 1:1, the rotating speed is 200rpm, and the time is 3 hours; 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 5 hours at 450 ℃ in air, and then heating to 900 ℃ for sintering for 20 hours 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% based on the mass of the layered oxide of 100%, then placing the mixture in a muffle furnace, and sintering the mixture at 800 ℃ for 5 hours in a nitrogen atmosphere to obtain the layered oxide anode material.
Comparative example 4
A layered oxide positive electrode material and a preparation method thereof are provided, 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 At 1.545:1Carrying out wet ball milling at a molar ratio of 0.5:0.5, wherein an organic solvent adopted by the wet ball milling is ethanol (the mass ratio of solid matters to ethanol is 1:1.2), the ball-material ratio is 1:1, the rotating speed is 200rpm, and the time is 3 hours; 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 5 hours at 450 ℃ in air, and then heating to 900 ℃ for sintering for 20 hours to obtain a layered oxide;
(3) Adding 3g of trimethylaluminum (2.0M in toluene, purchased from microphone) into 150mL of toluene, stirring uniformly, adding 150g of layered oxide obtained in the 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 sintering at 200 ℃ in vacuum for 3h to obtain Al 2 O 3 And (3) coating the layered oxide, namely the layered oxide positive electrode material.
The layered oxide cathode materials provided in examples 1 to 10 and comparative examples 1 to 4 were tested for performance by the following method:
1. crystal structure test
The crystal structure of the layered oxide cathode material was tested by using an X-ray diffractometer (XRD, shimadzu, XRD 6100), wherein the XRD pattern of the layered oxide cathode material provided in example 1 is shown in fig. 1, and it is known from fig. 1 that the layered oxide cathode material has good crystallinity and no impurity peak.
2. Elemental analysis
The method for preparing the sample comprises the steps of adopting an inductively coupled plasma emission spectrometer (ICP, agilent 5100) to perform elemental analysis on the layered oxide anode material: 1.0g of a sample to be measured is taken and placed in a 50mL PTFE beaker, 3mL of concentrated nitric acid and 9mL of hydrochloric acid are added into the PTFE beaker, and after heating for 30min by a hot plate at 260 ℃, the mixture is filtered and transferred to a 100mL volumetric flask for constant volume measurement; ICP test was performed on the above test solution, and the results are shown in Table 1:
TABLE 1
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3. Electrochemical performance test
Assembling a sodium ion button cell by adopting a layered oxide positive electrode material to be detected: mixing a layered oxide positive electrode material, conductive carbon black (Super P) and polyvinylidene fluoride (PVDF) according to a mass ratio of 8:1:1, adding an organic solvent N-methyl pyrrolidone (NMP) to obtain slurry with a solid content of 33%, and then coating the slurry on an aluminum foil to form a positive plate; assembling the prepared positive electrode plate and a sodium metal plate into a sodium ion button cell, and dissolving sodium perchlorate with the concentration of 1M in Propylene Carbonate (PC)/fluoroethylene carbonate (FEC) (the mass ratio is 97:3, shenzhen friend grinding) to obtain an electrolyte; after the electricity buckling assembly is completed, capacity, circulation and other tests are carried out on the blue battery test system according to the following steps: standing for 2h; constant current charge and discharge, the charge and discharge voltage interval is 2.0-4.3V, the circulation 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
According to the performance test data combined with Table 2, compared with the layered oxide positive electrode material (comparative example 1) prepared by a conventional solid phase method, the preparation method provided by the invention is characterized in that a carbonaceous material is introduced, the structural stability and electrochemical performance of the obtained layered oxide positive electrode material are obviously improved through the cooperation and synergistic effect of the design of raw materials and a specific process, the specific capacities of the layered oxide positive electrode material serving as positive electrode active materials at 0.1C, 0.5C, 1.0C, 2.0C and 5.0C are respectively 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, the capacity retention rate at 0.5C is 82.1-88.4% and the capacity retention rate at 2.0C cycle 300 is 60.1-68.6%, and particularly the excellent cycle performance at high multiplying power is proved that the layered oxide positive electrode material has obvious breakthrough in structural stability.
In the preparation method provided by the invention, a series of carbonization and oxidation reactions are carried out on the carbonaceous material with specific dosage in the sintering process, so that the oxygen distribution condition on the surface of the layered oxide is regulated and controlled to form an oxygen-deficient stable phase, an oxygen-deficient coating layer which is the same as the components of the bulk material, tightly combined and stable in structure is generated in situ, and the obtained layered oxide anode material has a structure gradually transiting 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 carbonaceous material of comparative example 3 forms a carbon coating layer during sintering, which can improve the conductivity of the material to some extent and the specific capacity, but cannot form a uniform oxygen-deficient coating layer, so that the cycle performance is not significantly improved; comparative example 4 formation of Al on layered oxide 2 O 3 The coating layer has improved cycle performance compared with the uncoated layered oxide, but has interface problems due to the different compositions of the coating layer and the layered oxide body, resulting in lower capacity retention after multiple cycles at high magnification and poor cycle performance improvement effect.
The applicant states that the present invention is illustrated by the above examples as well as methods of making and using the layered oxide cathode material of the present invention, but the present invention is not limited to the above process steps, i.e., it is not meant that the present invention must be practiced in dependence upon the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (30)
1. A kind of havingThe preparation method of the layered oxide positive electrode material with the homogeneous oxygen-deficient coating layer structure is characterized in that the layered oxide positive electrode material is NaxMO 2 Wherein x is more than 0 and less than or equal to 1, and M is selected from any one or a combination of at least two of Ni, co, mn, fe, cu, ti, sn;
the preparation method comprises the following steps: mixing a sodium source, an M metal source and a carbonaceous material to obtain a mixture; sintering the mixture under the aerobic condition to obtain the layered oxide cathode material;
The sintering comprises a first-stage sintering and a second-stage sintering which are sequentially carried out, wherein the temperature of the first-stage sintering is less than that of the second-stage sintering;
the carbonaceous material comprises any one or a combination of at least two of saccharide compounds, polystyrene and polydopamine; the saccharide compound is any one or the combination of at least two of glucose, sucrose, chitosan, maltose and starch;
the mass of the carbonaceous material is 0.2 to 5.5% based on 100% of the mass of the layered oxide made of the sodium source and the M metal source.
2. The method of claim 1, wherein the sodium source is sodium hydroxide and/or sodium salt.
3. The method according to claim 2, wherein the sodium source is any one or a combination of at least two of sodium hydroxide, sodium carbonate, sodium acetate, sodium sulfate, sodium nitrate, and sodium chloride.
4. The method of claim 1, wherein the M metal source comprises a nickel source and a manganese source and comprises at least one of an iron source, a cobalt source, a copper source, a titanium source, and a tin source.
5. The method of claim 4, wherein the M metal source is a combination of a nickel source, a manganese source, and an iron source.
6. The method according to claim 4, wherein the nickel source is any one or a combination of at least two of nickel oxide, nickel hydroxide and nickel salt.
7. The method according to claim 4, wherein the manganese source is manganese oxide and/or manganese salt.
8. The method according to claim 4, wherein the iron source is any one or a combination of at least two of iron oxide, iron salt and ferrous salt.
9. The production method according to claim 1, wherein the mass of the carbonaceous material is 1 to 5% based on 100% of the mass of the layered oxide produced from the sodium source and the M metal source.
10. The method of claim 1, wherein the method of mixing is ball milling.
11. The method of claim 10, wherein the method of mixing is wet ball milling.
12. The method of claim 10, wherein the ball milling is performed in the presence of an organic solvent, the organic solvent comprising an alcohol solvent and/or a ketone solvent.
13. The method according to claim 10, wherein the ball-milling ratio is (0.5-2): 1.
14. The method of claim 10, wherein the rotational speed of the ball mill is 100-350 rpm.
15. The method of claim 10, wherein the ball milling is performed for a period of time ranging from 1 to 5 h.
16. The method of claim 10, further comprising a step of drying after the ball milling is completed.
17. The method of claim 16, wherein the drying temperature is 60-100 ℃.
18. The method of claim 16, wherein the drying is for a period of time ranging from 1 to 6 h.
19. The method of claim 1, wherein the first stage sintering is at a temperature of 300-600 ℃.
20. The method of claim 1, wherein the first stage sintering is performed for a time period of 2-7 h.
21. The method of claim 1, wherein the second stage sintering is performed at a temperature of 800-950 ℃.
22. The method of claim 1, wherein the second stage sintering is performed for a period of time ranging from 10 to 30 h.
23. The preparation method according to claim 1, characterized in that the preparation method comprises the steps of:
(1) Mixing a sodium source, an M metal source and a carbon-containing material through wet ball milling, and drying after uniformly mixing to obtain a mixture;
wherein the M metal source comprises a nickel source and a manganese source and any one of an iron source, a cobalt source, a copper source, a titanium source and a tin source; the carbonaceous material comprises any one or a combination of at least two of saccharide compounds, polystyrene and polydopamine; the saccharide compound is any one or the combination of at least two of glucose, sucrose, chitosan, maltose and starch; the mass of the carbonaceous material is 0.2-5.5% based on the mass of the layered oxide made of the sodium source and the M metal source being 100%;
the ball-material ratio of the wet ball milling is (0.5-2) 1, the rotating speed is 100-350 rpm, and the time is 1-5 h;
(2) Sequentially performing first-stage sintering and second-stage sintering on the mixture obtained in the step (1) under the aerobic condition to obtain the layered oxide cathode material;
wherein the temperature of the first stage sintering is 300-600 ℃ and the time is 2-7 h; the temperature of the second stage sintering is 800-950 ℃ and the time is 10-30 h.
24. A layered oxide cathode material having a homogeneous oxygen-deficient coating layer structure, characterized in that the layered oxide cathode material is prepared by the preparation method according to any one of claims 1 to 23.
25. The layered oxide cathode material of claim 24, wherein the layered oxide cathode material is NaxMO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x is 0.5-1, and M is selected from any one or a combination of at least two of Ni, co, mn, fe, cu, ti, sn.
26. The layered oxide cathode material of claim 25, wherein the layered oxide cathode material is NaxNiyMnzM' (1-y-z) O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein y is more than 0 and less than 1, z is more than 0 and less than 1, and M' is selected from any one or a combination of at least two of Co, fe, cu, ti, sn.
27. The layered oxide cathode material of claim 26, wherein the layered oxide cathode material is NaxNiyMnzFe (1-y-z) O 2 。
28. Use of the layered oxide cathode material having a homogeneous oxygen-deficient coating layer structure according to any one of claims 24 to 27 in an electrochemical device.
29. The use according to claim 28, wherein the electrochemical device is a sodium ion battery or a capacitor.
30. A sodium ion battery comprising a layered oxide cathode material having a homogeneous oxygen-deficient coating structure as defined in any one of claims 24-27.
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