CN116081710A - Potassium-doped nickel-manganese-copper ternary layered oxide and preparation method and application thereof - Google Patents

Potassium-doped nickel-manganese-copper ternary layered oxide and preparation method and application thereof Download PDF

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CN116081710A
CN116081710A CN202310143211.XA CN202310143211A CN116081710A CN 116081710 A CN116081710 A CN 116081710A CN 202310143211 A CN202310143211 A CN 202310143211A CN 116081710 A CN116081710 A CN 116081710A
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potassium
manganese
salt
copper
ternary layered
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刘启明
林野
刘一睿
杨希国
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Douzhu Science And Technology Wuhan Co ltd
Wuhan University WHU
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    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract

The invention discloses a potassium-doped nickel-manganese-copper ternary layered oxide and a preparation method and application thereof, and belongs to the technical field of sodium ion battery anode materials. The chemical formula of the oxide is Na 0.67‑x K x Ni 0.22 Mn 0.67 Cu 0.11 O 2 Wherein x is more than 0.01 and less than or equal to 0.10. Firstly, mixing sodium salt, potassium salt, nickel salt, manganese salt and copper salt according to a proportion, then adding citric acid and adjusting the PH value to 7-8 by ammonia water to obtain a sol product; drying the obtained sol product to obtain a gel product; finally, the gel is producedGrinding the materials into powder, presintering in an air atmosphere, sintering, cooling and grinding to obtain the potassium-doped nickel-manganese-copper ternary layered oxide. The invention improves the cycling stability of the material and further improves the electrochemical performance of the material by doping the potassium element. The initial discharge specific capacity of the oxide reaches 120.3mAh/g under the condition of 100mA/g of current density, and the capacity retention rate is still 84.5% after 100 circles of circulation.

Description

Potassium-doped nickel-manganese-copper ternary layered oxide and preparation method and application thereof
Technical Field
The invention belongs to the technical field of sodium ion battery anode materials, and particularly relates to a potassium-doped nickel-manganese-copper ternary layered oxide, and a preparation method and application thereof.
Background
In recent years, with rapid development of technology, energy problems are increasingly emphasized, and energy storage is particularly important. Lithium ion batteries have achieved great success in the past twenty years due to the advantages of large energy, long life, high stability and the like, and have been widely used in the fields of electronic equipment, electric automobiles, electrochemical energy storage and the like. However, lithium element has low natural abundance and uneven distribution, and cannot become a key of large-scale energy storage. Sodium ion batteries of the same family as lithium are slowly paid attention to by researchers, sodium has chemical properties close to those of metallic lithium, and has abundant global reserves, wide distribution and low cost. The positive electrode of the sodium ion battery is expected to become a new generation of high-performance low-cost energy storage technology.
The sodium ion battery mainly comprises a positive electrode material, a negative electrode material, a diaphragm, electrolyte, a current collector and a battery shell, and the working principle is similar to that of a lithium ion battery, and in the practical application process, compared with lithium, sodium has higher quality and larger radius, and can cause larger volume shrinkage and expansion during deintercalation, so that great challenges are brought to the design of the positive electrode material. At present, the anode electrode material of the sodium ion battery can be mainly divided into transition metal oxides, polyanions, prussian blue and partial organic compounds. Among them, transition metal oxides are considered as the most potential positive electrode materials for sodium ion batteries because of their higher theoretical specific capacity. The transition metal oxide can be represented by the general formula Na x MeO 2 (x is more than 0 and less than or equal to 1, me comprises Mn, fe, co, ni, cu and other transition metal elements),specifically, it is classified into tunnel transition metal oxides and layered transition metal oxides. The layered metal oxide is a layered structure formed by alternately arranging transition metal layers and alkali metal layers, wherein the transition metal layers are formed by repeatedly MO 6 Octahedral co-prismatic connection is formed, na + Then an alkali metal layer is formed between the transition metal layers. Layered metal oxides can be classified into P2 type (Na ion occupies MO 6 Prismatic sites) and O3 type (Na ion occupying MO 6 Octahedral sites).
Manganese-based layered transition metal oxide is considered to be the most potential positive electrode material for sodium ion batteries for practical use because of low cost of manganese element, wherein P2-Na 0.67 Ni 0.33 Mn 0.67 O 2 As classical manganese-based layered transition metal oxides, there is a great deal of attention because of their high theoretical specific capacity and high operating voltage. But P2-Na 0.67 Ni 0.33 Mn 0.67 O 2 It is still difficult to put into practical use for the following reasons: (1) Mn (Mn) 3+ The Jahn-Teller effect of (a); (2) an ordered arrangement of sodium ions and vacancies; (3) irreversible phase transition of P2-O2 charged to 4.2V or more. Huang Zhixiong et al synthesized Ni and Cu substituted Mn P2-Na by hydrothermal method 0.67 Mn 0.7 Ni 0.2 Cu 0.1 O 2 Sodium ion battery positive electrode layered oxide due to Ni 2+ /Ni 4+ And Cu 2+ /Cu 3+ Has a high oxidation-reduction potential, so that it is not easily compatible with H in air 2 O and CO 2 The reaction, the doping energy of Ni and Cu provides capacity, and relieves the Jahn-Teller effect of Mn and inhibits dissolution of manganese, and the prepared material is 100 mA.g -1 The initial discharge capacity is up to 129.6 mAh.g -1 Has excellent electrochemical performance. But the capacity retention of this material after 50 cycles was only about 77.6%.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the potassium-doped nickel-manganese-copper ternary layered oxide which has high specific capacity and good cycle stability. Specifically, the method is realized by the following technology.
Potassium doped nickel-manganese-copper ternary layered oxide with chemical formula of Na 0.67- x K x Ni 0.22 Mn 0.67 Cu 0.11 O 2 Wherein x is more than 0.01 and less than or equal to 0.10.
Preferably, the oxide has the formula Na 0.61 K 0.06 Ni 0.22 Mn 0.67 Cu 0.11 O 2 Or Na (or) 0.57 K 0.1 Ni 0.22 Mn 0.67 Cu 0.11 O 2 。
The invention also aims to provide a preparation method of the potassium-doped nickel-manganese-copper ternary layered oxide, which specifically comprises the following steps:
s1, according to the chemical formula Na 0.67-x K x Ni 0.22 Mn 0.67 Cu 0.11 O 2 The molar ratio of Na, K, ni, mn and Cu elements is measured, sodium salt, potassium salt, nickel salt, manganese salt and copper salt are dissolved in deionized water, then citric acid is added, stirring is carried out for 2-6 hours at 60-80 ℃, finally ammonia water is added dropwise to adjust the PH value of the solution to 7-8, and sol product A is obtained;
s2, drying the sol product A prepared in the step S1 to obtain a gel product B;
s3, grinding the gel product B prepared in the step S2 into powder, presintering in an air atmosphere, sintering, cooling and grinding to obtain the potassium-doped nickel-manganese-copper ternary layered oxide.
Preferably, the sodium salt, potassium salt, nickel salt, manganese salt and copper salt in step S1 are the corresponding citrate, acetate or carbonate salts.
Preferably, the drying time in step S2 is 12-24 hours and the drying temperature is 80-120 ℃.
Preferably, the presintering conditions in step S3 are calcination at 350-550 ℃ for 6-8 hours, and the sintering conditions are sintering at 800-1000 ℃ for 12-16 hours.
Further preferably, the pre-firing condition in step S3 is calcination at 450 ℃ for 6 hours, and the sintering condition is sintering at 900 ℃ for 12 hours.
The invention also aims to provide application of the potassium-doped nickel-manganese-copper ternary layered oxide in preparing a sodium ion battery anode material.
Compared with the prior art, the invention has the following advantages:
(1) The invention uses potassium and sodium co-doping method, potassium ion replaces part of sodium ion occupying prismatic position, which expands sodium ion layer spacing, and at the same time, plays a supporting role, stabilizes crystal structure, improves material circulation stability, and further improves electrochemical performance of the material. Na prepared by the invention 0.67-x K x Ni 0.22 Mn 0.67 Cu 0.11 O 2 The initial discharge specific capacity of the oxide is up to 120.3mAh/g under the condition of 100mA/g current density, and the capacity retention rate is still 84.5% after 100 circles of circulation.
(2) The preparation method of the potassium-doped nickel-manganese-copper ternary layered oxide provided by the invention is simple to operate and good in repeatability; according to the method, the liquid phase synthesis precursor is combined with grinding and calcining, so that the potassium element can be uniformly doped into the nickel-manganese-copper ternary layered oxide, the prepared material is smooth in surface, uniform in particle size and excellent in specific capacity and cycling stability.
Drawings
FIG. 1 is Na prepared in examples 1-2 and comparative example 1 0.61 K 0.06 Ni 0.22 Mn 0.67 Cu 0.11 O 2 、Na 0.57 K 0.1 Ni 0.22 Mn 0.67 Cu 0.11 O 2 And Na (Na) 0.67 Ni 0.22 Mn 0.67 Cu 0.11 O 2 X-ray diffraction (XRD) pattern of the oxide;
FIG. 2 is a Na prepared in example 1 0.61 K 0.06 Ni 0.22 Mn 0.67 Cu 0.11 O 2 Scanning Electron Microscope (SEM) images of the oxide;
FIG. 3 is a Na prepared in example 2 0.57 K 0.1 Ni 0.22 Mn 0.67 Cu 0.11 O 2 Scanning Electron Microscope (SEM) images of the oxide;
FIG. 4 is a Na prepared in comparative example 1 0.67 Ni 0.22 Mn 0.67 Cu 0.11 O 2 Scanning Electron Microscope (SEM) images of the oxide;
FIG. 5 is a Na prepared in example 1 0.61 K 0.06 Ni 0.22 Mn 0.67 Cu 0.11 O 2 A first three-turn constant current charge-discharge (GCD) plot of oxide;
FIG. 6 is a Na prepared in example 2 0.57 K 0.1 Ni 0.22 Mn 0.67 Cu 0.11 O 2 A first three-turn constant current charge-discharge (GCD) plot of oxide;
FIG. 7 is a Na prepared in comparative example 1 0.67 Ni 0.22 Mn 0.67 Cu 0.11 O 2 A first three-turn constant current charge-discharge (GCD) plot of oxide;
FIG. 8 is a graph showing constant current charge-discharge cycle characteristics of the oxides prepared in examples 1-2 and comparative example 1.
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are only some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by one of ordinary skill in the art without undue burden on the person of ordinary skill in the art based on embodiments of the present invention, are within the scope of the present invention.
The sodium salt, potassium salt, nickel salt, manganese salt and copper salt have little influence on the performance of the product, and can be corresponding citrate, acetate or carbonate, and sodium citrate, potassium citrate, nickel acetate, manganese acetate and copper acetate in the following examples and comparative examples are only examples and are not intended to limit the scope of the invention; the sodium citrate, the potassium citrate, the nickel acetate, the manganese acetate, the copper acetate, the citric acid and the ammonia water are all commercial products.
Example 1
The present example provides a potassium-doped ternary layered nickel-manganese-copper oxide having the chemical formula Na 0.61 K 0.06 Ni 0.22 Mn 0.67 Cu 0.11 O 2 The preparation method comprises the following steps:
s1, according to the synthesis of 1g Na 0.61 K 0.06 Ni 0.22 Mn 0.67 Cu 0.11 O 2 Weighing sodium citrate, potassium citrate, nickel acetate, manganese acetate and copper acetate according to the required molar ratio, dissolving in 100ml of deionized water, adding 1g of citric acid, stirring at 60 ℃ for 6 hours, and finally dropwise adding ammonia water to adjust the pH value of the solution to 8 to obtain a sol product A;
s2, placing the sol product A prepared in the step S1 in a drying oven to be dried at 80 ℃ for 12 hours to obtain a gel product B;
s3, manually grinding the gel product B obtained in the step S2 into powder, then placing the powder in a muffle furnace, presintering the powder at 450 ℃ for 6 hours, calcining the powder at 900 ℃ for 12 hours, naturally cooling, and manually grinding the powder to obtain the final product of the potassium-doped nickel-manganese-copper ternary layered oxide.
Example 2
The present example provides a potassium-doped ternary layered nickel-manganese-copper oxide having the chemical formula Na 0.57 K 0.1 Ni 0.22 Mn 0.67 Cu 0.11 O 2 The preparation method is basically the same as that of example 1, except that: sodium citrate, potassium citrate, nickel acetate, manganese acetate and copper acetate in the molar ratio of Na 0.57 K 0.1 Ni 0.22 Mn 0.67 Cu 0.11 O 2 The desired molar ratio.
Example 3
This example provides a potassium-doped ternary layered nickel-manganese-copper oxide of the same chemical formula as example 1, na 0.61 K 0.06 Ni 0.22 Mn 0.67 Cu 0.11 O 2 The preparation method is basically the same as that of example 1, except that: the presintering condition in the step S3 is presintering for 8 hours at 350 ℃; the calcination conditions were calcination at 800℃for 16h.
Comparative example 1
The comparative example provides a ternary layered oxide of nickel manganese copper having the chemical formula Na 0.67 Ni 0.22 Mn 0.67 Cu 0.11 O 2 Preparation thereofThe process is essentially the same as in example 1, except that: the molar ratio of sodium citrate, nickel acetate, manganese acetate and copper acetate is Na 0.67 Ni 0.22 Mn 0.67 Cu 0.11 O 2 The desired molar ratio.
Application example 1
The oxides prepared in examples 1-2 and comparative example 1 were mixed with a conductive agent (acetylene black) and a binder (polyvinylidene fluoride) in a mass ratio of 7:2:1, and a proper amount of N-methylpyrrolidone was added and ultrasonically dispersed to prepare a thick paste, which was coated on an aluminum foil and vacuum-dried for 12 hours, and then pressed into a pole piece. Sodium sheet is used as positive electrode, the prepared oxide is used as negative electrode, glass fiber is used as diaphragm, naClO 4 Button cells were assembled for electrolyte and constant current charge and discharge tests were performed.
As can be seen from the XRD patterns shown in FIG. 1, the oxides obtained in examples 1-2 and comparative example 1 are each having P6 3 The P2 type lamellar structure of the mmc space group has sharp diffraction peak, obvious splitting and no other obvious impurity peak.
As can be seen from the SEM images shown in FIGS. 2-4, the oxides prepared in examples 1-2 and comparative example 1 were each of a layered structure, and the particle sizes were each 2 μm to 5. Mu.m.
As can be seen from the first three constant current charge-discharge graphs shown in fig. 5 to 7, the first three discharge curves and the second and third charge curves of the oxides prepared in examples 1 and 2 are substantially coincident, indicating that the prepared oxides are excellent in cycle stability. The first three discharge curves and the second and third charge curves of the oxide prepared in comparative example 1 are obviously misaligned, which indicates that the cycle stability of the prepared oxide is poor.
FIG. 8 is a graph showing constant current charge-discharge cycle characteristics of the oxides prepared in examples 1-2 and comparative example 1, from which it can be seen that Na prepared in example 1 0.61 K 0.06 Ni 0.22 Mn 0.67 Cu 0.11 O 2 The oxide has an initial specific discharge capacity of 120.3mAh/g at a current density of 100mA/g and a capacity retention of 84.5% after 100 cycles; na prepared in example 2 0.57 K 0.1 Ni 0.22 Mn 0.67 Cu 0.11 O 2 The oxide has an initial specific discharge capacity of 111.1mAh/g at a current density of 100mA/g and a capacity retention of 87.4% after 100 cycles; comparative example 1 prepared Na 0.67 Ni 0.22 Mn 0.67 Cu 0.11 O 2 The oxide had an initial specific discharge capacity of 124.4mAh/g at a current density of 100mA/g and a capacity retention of 78.1% after 100 cycles.
As can be seen from comparative examples 1-2 and comparative example 1, the doping of potassium ions significantly improves the cycle stability of the nickel-manganese-copper ternary layered oxide positive electrode material, na obtained in example 1 0.61 K 0.06 Ni 0.22 Mn 0.67 Cu 0.11 O 2 The oxide has the best comprehensive electrochemical performance.
The above detailed description describes in detail the practice of the invention, but the invention is not limited to the specific details of the above embodiments. Many simple modifications and variations of the technical solution of the present invention are possible within the scope of the claims and technical idea of the present invention, which simple modifications are all within the scope of the present invention.

Claims (8)

1. A potassium-doped nickel-manganese-copper ternary layered oxide is characterized in that the chemical formula of the oxide is Na 0.67- x K x Ni 0.22 Mn 0.67 Cu 0.11 O 2 Wherein x is more than 0.01 and less than or equal to 0.10.
2. The potassium-doped nickel-manganese-copper ternary layered oxide according to claim 1, wherein the oxide has the formula Na 0.61 K 0.06 Ni 0.22 Mn 0.67 Cu 0.11 O 2 Or Na (or) 0.57 K 0.1 Ni 0.22 Mn 0.67 Cu 0.11 O 2 。
3. The method for preparing the potassium-doped nickel-manganese-copper ternary layered oxide according to claim 1, which is characterized by comprising the following steps:
s1, according to the chemical formula Na 0.67-x K x Ni 0.22 Mn 0.67 Cu 0.11 O 2 The molar ratio of Na, K, ni, mn and Cu elements is measured, sodium salt, potassium salt, nickel salt, manganese salt and copper salt are dissolved in deionized water, then citric acid is added, stirring is carried out for 2-6 hours at 60-80 ℃, finally ammonia water is added dropwise to adjust the PH value of the solution to 7-8, and sol product A is obtained;
s2, drying the sol product A prepared in the step S1 to obtain a gel product B;
s3, grinding the gel product B prepared in the step S2 into powder, presintering in an air atmosphere, sintering, cooling and grinding to obtain the potassium-doped nickel-manganese-copper ternary layered oxide.
4. The method of claim 3, wherein the sodium salt, potassium salt, nickel salt, manganese salt and copper salt in step S1 are citrate, acetate or carbonate salts.
5. The method for preparing a potassium-doped nickel-manganese-copper ternary layered oxide according to claim 3, wherein the drying time in the step S2 is 12-24 hours, and the drying temperature is 80-120 ℃.
6. The method for preparing a potassium-doped nickel-manganese-copper ternary layered oxide according to claim 3, wherein the pre-sintering condition in the step S3 is calcination at 350-550 ℃ for 6-8 hours, and the sintering condition is sintering at 800-1000 ℃ for 12-16 hours.
7. The method for preparing a potassium-doped nickel-manganese-copper ternary layered oxide according to claim 3, wherein the pre-firing condition in step S3 is calcination at 450 ℃ for 6 hours and the sintering condition is sintering at 900 ℃ for 12 hours.
8. The use of the potassium-doped nickel-manganese-copper ternary layered oxide prepared by the preparation method of any one of claims 3 to 7 in the preparation of a sodium ion battery anode material.
CN202310143211.XA 2023-02-21 2023-02-21 Potassium-doped nickel-manganese-copper ternary layered oxide and preparation method and application thereof Pending CN116081710A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117658243A (en) * 2024-01-31 2024-03-08 成都大学 Potassium ion battery anode material and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117658243A (en) * 2024-01-31 2024-03-08 成都大学 Potassium ion battery anode material and preparation method thereof
CN117658243B (en) * 2024-01-31 2024-04-23 成都大学 Potassium ion battery anode material and preparation method thereof

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