CN113526560A - Sodium-potassium co-embedded metal oxide cathode material and preparation method thereof - Google Patents
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Abstract
The invention discloses a sodium-potassium co-embedded metal oxide cathode material and a preparation method thereof, wherein the preparation method comprises the following steps: 1) taking potassium salt and transition metal salt as raw materials, and preparing a P3-phase potassium-rich layered metal oxide by a high-temperature solid phase method; 2) mixing the potassium-rich layered metal oxide powder and a sodium simple substance in an inert atmosphere according to the required sodium insertion amount, dropwise adding a sodium ion electrolyte to wet the mixture, and fully grinding to obtain uniform slurry; 3) and standing the slurry in an inert atmosphere to enable potassium-rich layered metal oxide powder to fully react with sodium simple substances, cleaning and centrifugally separating, and drying the obtained precipitate to obtain the sodium-potassium co-embedded metal oxide cathode material. The preparation method is mild and simple and convenient to operate, and the prepared sodium-potassium co-embedded metal oxide anode material has the advantages of high diffusion coefficient, good rate capability, good stability and the like, and is suitable for anode materials of electrochemical energy storage devices.
Description
Technical Field
The invention belongs to the technical field of energy storage material preparation, and particularly relates to a sodium-potassium co-embedded metal oxide positive electrode material and a preparation method thereof.
Background
Due to high theoretical capacity, wide material source and simple preparation method, the layered transition metal oxide has wide application in the fields of batteries, supercapacitors, electrocatalysts and the like, for example, lithium cobaltate and ternary lithium battery materials in lithium ion batteries belong to the category. Sodium-rich layered oxide positive electrode materials, e.g. Na0.7MnO2、 Na0.67Ni0.33Mn0.67O2、Na0.67Fe0.5Mn0.5O2And the like, and is also a positive electrode material with the most application prospect. But due to the radius of sodium ions
Lithium ion
Further, since it is difficult to intercalate and deintercalate sodium ions into and from an electrode material, it is necessary to improve the capacity and rate capability of the electrode material by promoting the diffusion of sodium ions by a modification means. There are documents in the past[2]The potassium ions with larger sizes are embedded into the sodium-rich layered oxide cathode material by a high-temperature solid phase method, and the interlayer spacing of the material is enlarged, so that the diffusion rate of the sodium ions is improved.
However, this part of the research results are not ideal because potassium ions are larger than sodium ions in size and are more difficult to be embedded into the layered oxide, and even under the condition of high-temperature sintering, the number of potassium ions embedded into the material is less than 5%, so that the performance of the material is difficult to be remarkably improved.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a sodium-potassium co-embedded metal oxide positive electrode material and a preparation method thereof. The sodium-potassium co-intercalation metal oxide anode material is prepared by taking a potassium-rich layered oxide material as a base material and taking a sodium simple substance as a sodium intercalation agent and promoting the reaction by grinding at normal temperature. The sodium-potassium co-embedded metal oxide cathode material prepared by the invention has the advantages of high potassium ion embedding amount, large diffusion coefficient, high capacity and rate capability, and is a cathode material with good potential.
The invention adopts the following specific technical scheme:
in a first aspect, the invention provides a preparation method of a sodium-potassium co-embedded metal oxide positive electrode material, which comprises the following specific steps:
1) the P3 phase potassium-rich layered metal oxide (P3-K) is prepared by high-temperature solid phase method by using potassium salt and transition metal salt as raw materialsxTMO2Preferably, TM is one or more of Ni, Mn, Cu and Fe); the method can adopt a high-temperature solid phase method commonly used in the prior art to prepare P3-KxTMO2。
2) Weighing certain mass of potassium-rich layered metal oxide powder and sodium simple substance in an inert atmosphere according to the required sodium-embedding amount, mixing the weighed potassium-rich layered metal oxide powder and sodium simple substance, dropwise adding a small amount of sodium ion electrolyte to wet the mixture (potassium-rich layered metal oxide powder and sodium simple substance), and fully grinding to obtain uniform slurry; preferably, the sodium simple substance and P3-K can be adjusted according to the expected sodium insertion amountxTMO2The mass ratio of the powder is generally 1:5 to 1: 2;
3) standing the slurry in an inert atmosphere to enable potassium-rich layered metal oxide powder to fully react with sodium simple substance, cleaning and centrifugally separating, drying the obtained precipitate in a vacuum environment or a protective atmosphere to obtain the sodium-potassium co-embedded metal oxide cathode material (marked as Na)yKzTMO2)。
Preferably, the mixing molar ratio of the potassium salt to the transition metal salt is 1:1 to 1: 2.
Preferably, the sintering temperature in the high-temperature solid-phase method is 700 ℃ or higher.
Preferably, the potassium salt is one or more of carbonate, carbonate hydrate, acetate hydrate, oxalate or oxalate hydrate containing potassium ions; the transition metal salt is one or more of carbonate, carbonate hydrate, acetate hydrate, oxalate or oxalate hydrate containing transition metal ions.
Further, the transition metal is one or more of Ni, Mn, Cu and Fe.
Preferably, the sodium ion electrolyte is any commercial ester or ether solution containing sodium ions.
Further, the solute of the sodium ion electrolyte is sodium perchlorate NaClO4Or sodium hexafluorophosphate NaPF6The solvent is one of a mixed solution of ethylene carbonate and propylene carbonate in a volume ratio of 1: 2-2: 1, a mixed solution of ethylene carbonate and diethyl carbonate in a volume ratio of 1: 2-2: 1, and ethylene glycol dimethyl ether.
Preferably, the solute of the sodium ion electrolyte is sodium perchlorate NaClO4Or sodium hexafluorophosphate NaPF6The solvent is one of a mixed solution of ethylene carbonate and propylene carbonate in a volume ratio of 1: 2-2: 1, a mixed solution of ethylene carbonate and diethyl carbonate in a volume ratio of 1: 2-2: 1, and ethylene glycol dimethyl ether.
Preferably, in the step 2), the grinding time is more than 15 min; in the step 3), the standing time is more than 1 h.
Preferably, in the step 3), the slurry after sufficient reaction is washed with ethanol to remove excessive sodium.
In a second aspect, the invention provides a sodium-potassium co-intercalation metal oxide cathode material obtained by the preparation method of any one of the first aspect, wherein the crystal form of the sodium-potassium co-intercalation metal oxide cathode material is one or more of P2, P3 and O3 (mostly P2), sodium ions and potassium ions are mixed and embedded in a layered structure, the mole number of the potassium ions is not less than 10% of that of the sodium ions, and the sodium ion diffusion coefficient of the material is obviously improved compared with that of a layered oxide material only containing sodium.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts a potassium-rich layered oxide positive electrode material (namely, a potassium-rich layered metal oxide) as a base material, and sodium ions are embedded into the potassium-rich material (namely, the potassium-rich layered metal oxide) to prepare the sodium-potassium co-embedded positive electrode material (the sodium-potassium co-embedded metal oxide positive electrode material). Because the potassium ion size is large, the potassium-rich layered oxide has larger interlayer spacing, so the sodium ions are easy to be embedded into the potassium-rich material, the potassium content in the final product is greatly improved compared with the potassium content in the prior art, the K/Na molar ratio reaches more than 0.1, and the sodium-potassium co-embedding reaction can be completed at normal temperature without a high-temperature solid phase method. The sodium-potassium co-embedded metal oxide positive electrode material prepared by the method has good sodium ion diffusion dynamics, the diffusion coefficient is greatly increased, and the capacity and rate capability of the material are also remarkably improved.
Drawings
FIG. 1 shows Na-K co-inserted Na prepared in example 1xKyFe0.2Mn0.8O2Scanning electron microscope pictures of the anode material;
FIG. 2 shows Na-K co-inserted Na prepared in example 1xKyFe0.2Mn0.8O2An XRD spectrum of the anode material;
FIG. 3 shows Na-K co-inserted Na prepared in example 2xKyCu0.2Mn0.8O2Potentiostatic intermittent titration curve of the positive electrode material.
Detailed Description
The invention will be further elucidated and described with reference to the drawings and the detailed description. The technical features of the embodiments of the present invention can be combined correspondingly without mutual conflict.
Example 1
1) Taking ferrous oxalate (FeC)2O4) And manganese acetate ((CH)3COO)2Mn) as a transition metal salt, potassium acetate (CH)3COOK) as potassium salt.
2) Prepared by a high-temperature solid phase methodPotassium-rich layered metal oxides P3-K to P3 phasexFe0.2Mn0.8O2The method comprises the following steps: weighing 5mmol FeC2O4、20mmol(CH3COO)2Mn and 15mmol CH3COOK, grinding uniformly, placing into crucible, heating to 700 deg.C with muffle furnace at 2.5 deg.C/min, holding for 2 hr, taking out, and quenching in air to obtain P3-KxFe0.2Mn0.8O2(since K will evaporate a little, x here is about 0.5).
3) Sodium ions are intercalated by a grinding method, which comprises the following steps: 200mg of sodium blocks (simple sodium) and 800mg of P3-K prepared in step 2) were weighed in a glove box (i.e. under an inert atmosphere)xFe0.2Mn0.8O2Grinding and mixing the mixture in a mortar, and dropwise adding 1ml of NaClO4the/EC/DEC electrolyte (sodium ion electrolyte) was used to wet the mixture and milling was continued for 15 minutes until a uniform, viscous slurry was formed.
4) The slurry was allowed to stand in a glove box (i.e., under an inert atmosphere) for 1 hour, washed with absolute ethanol three times or more, and centrifuged to obtain a precipitate.
5) Drying the precipitate obtained by centrifugation in a vacuum drying oven at 60 ℃ overnight to obtain the Na-K co-embedded metal oxide cathode material NayKzFe0.2Mn0.8O2。
The chemical composition of the sodium-potassium co-intercalation metal oxide cathode material prepared in the embodiment is Na0.865K0.105Fe0.171Mn0.829O2Wherein the content z of the potassium ions reaches 0.105, the molar ratio of K/Na reaches 0.121, which is obviously higher than the content level of the potassium ions reported in the literature. A scanning electron microscope picture of the material is shown in fig. 1, from which it can be seen that the material has a polygonal granular structure. The XRD pattern of the material is shown in FIG. 2, from which it can be seen that the material has a P2 phase layered oxide structure, the leftmost peak corresponds to the (002) crystal plane of the material, and the interlayer spacing of the material after intercalation of potassium is
Not only the interlayer spacing of the sample without potassium
Higher and higher than the literature[1]Middle level
The material is in the range of 2.0-3.8V (vs. Na/Na)+Hereinafter the same) potential interval reaches 1.96 multiplied by 10-12cm2S, ratio of samples containing no potassium (. about.1X 10)-12cm2/s) is significantly improved and at a higher level than in the prior art.
Example 2
1) Taking copper acetate ((CH)3COO)2Cu) and manganese acetate ((CH)3COO)2Mn) as transition metal salt, potassium carbonate (K)2CO3) As the potassium salt.
2) Preparing P3-phase potassium-rich layered metal oxide P3-K by using a high-temperature solid-phase methodxCu0.2Mn0.8O2The method comprises the following steps: weighing 10mmol (CH)3COO)2Cu、40mmol(CH3COO)2Mn and 15mmol K2CO3Grinding uniformly, placing into a crucible, heating to 900 deg.C with a muffle furnace at a rate of 3 deg.C/min, holding for 1 hr, taking out, and quenching in air to obtain P3-KxCu0.2Mn0.8O2。
3) Sodium ions are intercalated by a grinding method, which comprises the following steps: 230mg of sodium blocks (simple sodium) and P3-1000mg K prepared by step 2) were weighed in a glove box (i.e. under inert atmosphere)xCu0.2Mn0.8O2Grinding and mixing the mixture in a mortar, and dropwise adding 1.5ml of NaClO4the/EC/PC electrolyte (sodium ion electrolyte) was used to wet the mixture and milling was continued for 15 minutes until a homogeneous, viscous slurry was formed.
4) The slurry was allowed to stand in a glove box (i.e., under an inert atmosphere) for 1 hour, washed with absolute ethanol three times or more, and centrifuged to obtain a precipitate.
5) The precipitate obtained by centrifugation is added inDrying in a vacuum drying oven at 60 ℃ overnight to obtain the Na-K co-embedded metal oxide anode material NayKzCu0.2Mn0.8O2。
The Na-K co-intercalation metal oxide cathode material prepared in this exampleyKzCu0.2Mn0.8O2Has similar characteristics to the material obtained in example 1, and has a specific component of Na0.7K0.1Cu0.2Mn0.8O2The molar ratio of K to Na is 1/7, and XRD characterization shows that the crystal structure of the material is P2 type oxide and the interlayer spacing is
The potentiostatic batch titration curve is shown in FIG. 3, from which it can be seen that the sodium ion diffusion coefficient of the material is 1.89X 10-12cm2S, and samples containing no potassium (. about.1X 10)-12cm2At a higher level than at the second level.
Example 3
1) Taking nickel acetate (Ni (CH)3COO)2·4H2O) and manganese oxalate (MnC)2O4) As the transition metal salt, potassium acetate (CH)3COOK) as potassium salt.
2) Preparing P3-phase potassium-rich layered metal oxide P3-K by using a high-temperature solid-phase methodxNi0.33Mn0.67O2The method comprises the following steps: weighing 10mmol (CH)3COO)2Ni、20mmol (CH3COO)2Mn and 15mmol K2CO3Grinding uniformly, placing into a crucible, heating to 900 deg.C with a muffle furnace at a rate of 3 deg.C/min, holding for 1 hr, taking out, and quenching in air to obtain P3-KxNi0.33Mn0.67O2。
3) Sodium ions are intercalated by a grinding method, which comprises the following steps: 100mg of sodium blocks (elemental sodium) and 500mg of P3-K prepared in step 2) were weighed in a glove box (i.e. under an inert atmosphere)xNi0.33Mn0.67O2Grinding and mixing the mixture in a ball mill tank, and dripping 0.5ml of NaPF6DME/FEC electrolyteSodium ion electrolyte) to wet the mixture and ball milled for 30 minutes using a mechanical ball milling method until a uniform, viscous slurry is formed.
4) The slurry was allowed to stand overnight in a glove box (i.e., under an inert atmosphere), washed with absolute ethanol three or more times, and filtered to obtain a precipitate.
5) Placing the precipitate obtained by centrifugation in a tubular furnace, introducing nitrogen to protect and heat to 160 ℃, heating for 2 hours to fully dry to obtain the Na-K co-embedded metal oxide anode material NayKzNi0.33Mn0.67O2。
In this example, the obtained sodium-potassium co-intercalation metal oxide cathode material nickel phosphate/gold nanoparticle composite aerogel Na is preparedyKzNi0.33Mn0.67O2Having similar characteristics to the material obtained in example 1, the composition of which is in particular Na0.67K0.11Ni0.33Mn0.67O2The molar ratio of K to Na is 1/6, and the XRD characterization shows that the crystal structure is mixed oxide of P2/O3 type, and the interlayer spacing is
The diffusion coefficient of sodium ion is 1.71X 10-12cm2S, and samples containing no potassium (. about.1X 10)- 12cm2At a higher level than at the second level.
The preparation method is suitable for various material systems such as nickel-manganese, iron-manganese, copper-manganese oxides and the like, and has certain universal applicability. The preparation method is mild, the operation is simple and convenient, and the prepared sodium-potassium co-embedded metal oxide anode material has the advantages of high diffusion coefficient, good rate capability, good stability and the like, and is suitable for anode materials of electrochemical energy storage devices.
The above-described embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, the technical scheme obtained by adopting the mode of equivalent replacement or equivalent transformation is within the protection scope of the invention.
The references cited in the present invention are as follows:
[1]Kai Wang et al.Electrochimica Acta 216(2016)51–57.
[2]Divya Sehrawat et al.CrystEngComm,2019,21,172。
Claims (10)
1. a preparation method of a sodium-potassium co-embedded metal oxide positive electrode material is characterized by comprising the following steps:
1) taking potassium salt and transition metal salt as raw materials, and preparing a P3-phase potassium-rich layered metal oxide by a high-temperature solid phase method;
2) mixing the potassium-rich layered metal oxide powder and a sodium simple substance in an inert atmosphere according to the required sodium insertion amount, dropwise adding a sodium ion electrolyte to wet the mixture, and fully grinding to obtain uniform slurry;
3) and standing the slurry in an inert atmosphere to enable potassium-rich layered metal oxide powder to fully react with sodium simple substances, cleaning and centrifugally separating, and drying the obtained precipitate to obtain the sodium-potassium co-embedded metal oxide cathode material.
2. The method for preparing a sodium-potassium co-embedded metal oxide cathode material as claimed in claim 1, wherein the mixing molar ratio of the potassium salt to the transition metal salt is 1: 1-1: 2.
3. The method for preparing a sodium-potassium co-embedded metal oxide positive electrode material as claimed in claim 1, wherein the sintering temperature of the high-temperature solid-phase method is 700 ℃ or higher.
4. The method for preparing the sodium-potassium co-intercalation metal oxide cathode material as claimed in claim 1, wherein the potassium salt is one or more of carbonate, carbonate hydrate, acetate hydrate, oxalate or oxalate hydrate containing potassium ions; the transition metal salt is one or more of carbonate, carbonate hydrate, acetate hydrate, oxalate or oxalate hydrate containing transition metal ions.
5. The method for preparing a sodium-potassium co-intercalation metal oxide cathode material as claimed in claim 1 or 4, wherein the transition metal is one or more of Ni, Mn, Cu, Fe.
6. The method for preparing the sodium-potassium co-embedded metal oxide cathode material as claimed in claim 1, wherein the sodium ion electrolyte is an ester or ether solution containing sodium ions.
7. The method for preparing the sodium-potassium co-embedded metal oxide cathode material as claimed in claim 1 or 6, wherein the solute of the sodium ion electrolyte is sodium perchlorate NaClO4Or sodium hexafluorophosphate NaPF6The solvent is one of a mixed solution of ethylene carbonate and propylene carbonate in a volume ratio of 1: 2-2: 1, a mixed solution of ethylene carbonate and diethyl carbonate in a volume ratio of 1: 2-2: 1, and ethylene glycol dimethyl ether.
8. The method for preparing a sodium-potassium co-embedded metal oxide positive electrode material according to claim 1, wherein in the step 2), the grinding time is more than 15 min; in the step 3), the standing time is more than 1 h.
9. The method for preparing the sodium-potassium co-embedded metal oxide cathode material as claimed in claim 1, wherein in the step 3), the slurry after sufficient reaction is washed by ethanol to remove excessive sodium.
10. The sodium-potassium co-intercalation metal oxide cathode material obtained by the preparation method of any one of claims 1-9, wherein the crystal form of the sodium-potassium co-intercalation metal oxide cathode material is one or more of P2, P3 and O3, and sodium ions and potassium ions are mixed and embedded in the layered structure.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115504525A (en) * | 2022-10-27 | 2022-12-23 | 澳门大学 | P2 type layered transition metal oxide and preparation method and application thereof |
| CN115947377A (en) * | 2023-01-10 | 2023-04-11 | 深圳华钠新材有限责任公司 | Preparation method and application of ferro-manganese-based sodium ion layered electrode material |
| CN116081708A (en) * | 2022-12-27 | 2023-05-09 | 华南师范大学 | Layered material, preparation method thereof, positive electrode material and sodium ion battery |
| WO2023193231A1 (en) * | 2022-04-08 | 2023-10-12 | 宁德时代新能源科技股份有限公司 | Secondary battery, preparation method for corresponding positive electrode active material, battery module, battery pack and electric device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104291350A (en) * | 2014-09-29 | 2015-01-21 | 中国地质大学（北京） | Process for synthesizing analcite from potassium feldspar powder by virtue of hydro-thermal alkaline method |
| JP2016110991A (en) * | 2014-11-27 | 2016-06-20 | 学校法人東京理科大学 | Positive electrode for sodium secondary battery and sodium secondary battery |
| CN110380024A (en) * | 2019-04-22 | 2019-10-25 | 南方科技大学 | Sodium transition metal oxide of P3 structure and preparation method thereof and sodium-ion battery |
| CN110446681A (en) * | 2016-05-19 | 2019-11-12 | 纪尧姆·兰伯特 | Sulfide electrolyte for metal processing and extracting |
| CN110504443A (en) * | 2018-05-16 | 2019-11-26 | 中国电力科学研究院有限公司 | Sodium magnesium manganese base layered oxide material, preparation method and the purposes appraised at the current rate with anion |
-
2021
- 2021-06-18 CN CN202110677937.2A patent/CN113526560B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104291350A (en) * | 2014-09-29 | 2015-01-21 | 中国地质大学（北京） | Process for synthesizing analcite from potassium feldspar powder by virtue of hydro-thermal alkaline method |
| JP2016110991A (en) * | 2014-11-27 | 2016-06-20 | 学校法人東京理科大学 | Positive electrode for sodium secondary battery and sodium secondary battery |
| CN110446681A (en) * | 2016-05-19 | 2019-11-12 | 纪尧姆·兰伯特 | Sulfide electrolyte for metal processing and extracting |
| CN110504443A (en) * | 2018-05-16 | 2019-11-26 | 中国电力科学研究院有限公司 | Sodium magnesium manganese base layered oxide material, preparation method and the purposes appraised at the current rate with anion |
| CN110380024A (en) * | 2019-04-22 | 2019-10-25 | 南方科技大学 | Sodium transition metal oxide of P3 structure and preparation method thereof and sodium-ion battery |
Non-Patent Citations (1)
| Title |
|---|
| DIVYA SEHRAWAT等: ""Investigation of K modified P2 Na0.7Mn0.8Mg0.2O2 as a cathode material for sodium-ion batteries"", 《CRYSTENGCOMM》 * |
Cited By (5)
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| WO2023193231A1 (en) * | 2022-04-08 | 2023-10-12 | 宁德时代新能源科技股份有限公司 | Secondary battery, preparation method for corresponding positive electrode active material, battery module, battery pack and electric device |
| CN115504525A (en) * | 2022-10-27 | 2022-12-23 | 澳门大学 | P2 type layered transition metal oxide and preparation method and application thereof |
| CN115504525B (en) * | 2022-10-27 | 2024-04-02 | 澳门大学 | P2 type layered transition metal oxide and preparation method and application thereof |
| CN116081708A (en) * | 2022-12-27 | 2023-05-09 | 华南师范大学 | Layered material, preparation method thereof, positive electrode material and sodium ion battery |
| CN115947377A (en) * | 2023-01-10 | 2023-04-11 | 深圳华钠新材有限责任公司 | Preparation method and application of ferro-manganese-based sodium ion layered electrode material |
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