CN113800495A - Novel potassium ion battery positive electrode material potassium vanadium fluorophosphate and preparation method and application thereof - Google Patents

Novel potassium ion battery positive electrode material potassium vanadium fluorophosphate and preparation method and application thereof Download PDF

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CN113800495A
CN113800495A CN202010537217.1A CN202010537217A CN113800495A CN 113800495 A CN113800495 A CN 113800495A CN 202010537217 A CN202010537217 A CN 202010537217A CN 113800495 A CN113800495 A CN 113800495A
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朱昌宝
张志波
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Sun Yat Sen University
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
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    • C01B25/455—Phosphates containing halogen
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    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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Abstract

The invention relates to a novel potassium ion battery anode material of vanadyl potassium fluophosphate and a preparation method and application thereof. The chemical formula of the potassium vanadium oxyfluoride phosphate is K3V2(PO4)2O2xF3‑2xWherein x is more than or equal to 0.005 and less than or equal to 1. The method utilizes the oxygen element to replace the fluorine element, so as to change the crystal structure and the transmission characteristic, and the finally obtained potassium vanadium oxyfluoride phosphate has the advantages of high energy-high power density, stable structure and long cycle life, reduces the cost and is beneficial to industrial production.

Description

Novel potassium ion battery positive electrode material potassium vanadium fluorophosphate and preparation method and application thereof
Technical Field
The invention belongs to the technical field of potassium ion battery anode materials, and particularly relates to a novel potassium ion battery anode material potassium vanadium oxyfluorophosphate as well as a preparation method and application thereof.
Technical Field
As the most widely used electronic products in portable electronic equipment, electric automobiles and partial power grid-level energy storage systems at present, lithium ion batteries have the advantages of high energy density, high charging and discharging speed, long cycle life and the like. However, its further application is limited by the scarcity of lithium resources. Although sodium resources are abundant in the earth's crust compared to lithium resources, the standard electrode potential for sodium is higher than that of lithium, which results in a lower energy density of the sodium-ion battery.
For the element potassium in the same main group, the standard electrode potential is closer to that of lithium, and the abundance of potassium resources on the earth is closer to that of sodium resources. Therefore, from the viewpoint of energy density and resource abundance, the potassium ion battery has bright prospect in future large-scale energy storage application.
At present, the development of the high-performance potassium ion battery cathode material is the key of further advancing practicability of the potassium ion battery. The positive electrode materials of potassium ion batteries can be roughly classified into four types: layered transition metal oxides, prussian blue and its analogues, organic compounds and polyanionic compounds. Among them, polyanionic compounds have high voltage, good structural stability and 3D ion channel for rapid transmission of potassium ions, and become one of the most promising materials at present.
Polyanion anode material vanadium potassium fluorophosphate with the chemical formula of K3V2(PO4)2F3Having a three-dimensional network frame structure capable of accommodating K+Can pass through quickly and can be at K+The structure is maintained stable during the de-intercalation and intercalation processes. But is limited by poor intrinsic electronic conductance, and the rate performance still has a larger promotion space. At present, the conventional modification means is mainly carbon coating, for example, CN201810037089.7 discloses a vanadium potassium fluorophosphate/carbon composite material, the electrical conductivity of the material is improved by compounding the vanadium potassium fluorophosphate and the carbon, and the material has the advantages of high capacity, long cycle life and high energy density, but the realization of the advantages is only based on the low current density of 23 mA/g; k is reported in literature (DOI:10.1016/j.ensm.2018.04.026)3V2(PO4)2F3Compounded with carbon, but it has a specific capacity of only-20 mAh/g remaining at a current density of 0.5A/g. In summary, at present K3V2(PO4)2F3Electrochemical performance remains to be improved.
Therefore, at present, polyanionic potassium electric anode materials which have high electrochemical activity and meet the requirements of practical application are still very lacking, and the development of novel high-performance polyanionic anode materials has important practical significance.
Disclosure of Invention
The invention aims to overcome the defects or shortcomings that the existing polyanion positive electrode material is low in electrochemical activity and cannot meet the requirements of practical application, and provides a novel potassium ion battery positive electrode material of potassium vanadium oxyfluorophosphate. The method utilizes the oxygen element to replace the fluorine element, so as to change the crystal structure and the transmission characteristic, and the finally obtained potassium vanadium oxyfluoride phosphate has the advantages of high energy-high power density, stable structure and long cycle life, reduces the cost and is beneficial to industrial production.
The invention also aims to provide a preparation method of the novel potassium ion battery positive electrode material potassium vanadium oxyfluorophosphate.
The invention also aims to provide application of the novel potassium ion battery positive electrode material potassium vanadium oxyfluoride phosphate in preparation of a potassium ion battery.
In order to realize the purpose of the invention, the invention adopts the following scheme:
a novel potassium ion battery anode material is fluorine oxygen potassium vanadium phosphate, and the chemical formula of the fluorine oxygen potassium vanadium phosphate is K3V2(PO4)2O2xF3-2xWherein x is more than or equal to 0.005 and less than or equal to 1.
The invention utilizes oxygen to replace fluorine, because the fluorine has stronger electronegativity, the adsorption effect on potassium ions is strong, and along with the replacement of the oxygen with lower electronegativity, the interaction with the potassium ions can be reduced, thereby accelerating the diffusion of the potassium ions. The finally obtained potassium vanadium oxyfluoride phosphate has the advantages of high energy-high power density, stable structure and long cycle life, reduces the cost and is beneficial to industrial production.
Specifically, the potassium vanadium oxyfluoride phosphate provided by the invention has two high potential platforms of 4.0V and 3.2V, and provides high energy density; under the high current density of 2A/g, the specific capacity of 65mAh/g still provides high power density; the capacity retention rate is 97 percent after 100 cycles under the current density of 100 mA/g.
Preferably, x is 1.
When x is 1, the potassium vanadium oxyfluorophosphate is specifically K3V2(PO4)2O2F。
The preparation method of the novel potassium ion battery anode material potassium vanadium fluorophosphate comprises the following steps: mixing Na3V2(PO4)2O2xF3-2xCarrying out ion exchange with potassium ions to obtain the potassium vanadium oxyfluorophosphate;
or uniformly mixing potassium salt, a vanadium source, a phosphorus source, a fluorine source and a reducing agent, heating to 400-800 ℃ in a protective atmosphere, and keeping the temperature for 1-24 hours to obtain the potassium vanadium oxyfluoride phosphate.
The novel potassium ion battery anode material of the vanadyl potassium fluoxyphosphate can be prepared by an ion exchange method and a direct synthesis method.
For the ion exchange method, mainly potassium ion and Na are used3V2(PO4)2O2xF3-2xExchanging sodium ions in the solution to obtain the product.
Na3V2(PO4)2O2xF3-2xCan be prepared by conventional method in the art, preferably, the Na3V2(PO4)2O2xF3-2xThe preparation method is characterized by comprising a hydrothermal method, a solid phase method, a sol-gel method, a spray drying method, an electrostatic spraying method or electrostatic spinning.
The invention also provides a hydrothermal method for preparing Na3V2(PO4)2O2xF3-2x. Specifically, sodium salt, vanadium source, phosphorus source and fluorine source (reducing agent is selected if necessary) are selected according to the molar ratio for preparation.
The oxygen replaces fluorine, and is mainly realized by regulating and controlling the valence state of a vanadium source in a final product. For example, when x is 1, V appears to be 4+When x is 0, V is represented by 3+The oxygen substitution proportion can be realized by regulating the valence state of the vanadium source. Specifically, a combination of vanadium sources with different valence states (in this case, the amount of the reducing agent is 0) can be selected, and vanadium source with high valence state plus the reducing agent can be selected to regulate and control vanadiumThe valence state of the source.
Preferably, the Na3V2(PO4)2O2xF3-2xPrepared by a hydrothermal method, wherein the hydrothermal method comprises the following steps:
s11: dissolving and mixing sodium salt, a vanadium source, a phosphorus source, a fluorine source and a carbon source to obtain a coprecipitated suspension;
s12: performing hydrothermal reaction on the suspension of S11 to obtain Na3V2(PO4)2O2xF3-2x。
More preferably, the temperature of the hydrothermal reaction is 30-200 ℃, and the time of the hydrothermal reaction is 5-120 h.
More preferably, the hydrothermal reaction further comprises the steps of filtering and drying.
The invention provides two ion exchange means simultaneously to obtain the potassium vanadium oxyfluorophosphate.
More preferably, the ion exchange process is: mixing Na3V2(PO4)2O2xF3-2xAnd (3) as the anode, taking a metal potassium sheet as the cathode, assembling the metal potassium sheet into a battery, and circulating for a plurality of circles under a certain current density until the sodium ions are completely replaced by potassium ions, thus obtaining the potassium vanadium oxyfluoride phosphate.
Specifically, Na is added3V2(PO4)2O2xF3-2xThe preparation method comprises the following steps of grinding and uniformly mixing a conductive agent (such as acetylene black) and a binder (such as PVDF), adding a proper amount of NMP to prepare electrode slurry, coating the electrode slurry on an aluminum foil, assembling the electrode slurry and a metal potassium sheet into a battery, and finally circulating for 5 circles under the condition that the current density is 10-100 mA/g.
More preferably, the ion exchange process is: mixing Na3V2(PO4)2O2xF3-2xMixing with potassium-containing salt (such as KBr, KCl, etc.) in high boiling point solvent (such as 1-hexanol), and heating and refluxing at the boiling point temperature of the solvent to perform ion exchange of K/Na, thereby obtaining the potassium vanadium oxyfluoride phosphate.
When the K/Na ratio is large enough (1.5: 1), the two can realize complete exchange.
Specifically, Na is added3V2(PO4)2O2xF3-2xAdded to a 5mol/L solution of KBr (K/Na ratio. gtoreq.1.5: 1) in 1-hexanol and refluxed at its boiling point (160 ℃).
For the direct synthesis, it preferably comprises the following steps: and (3) uniformly mixing potassium salt, a vanadium source, a phosphorus source, a fluorine source and a carbon source, heating to 400-800 ℃ under a protective atmosphere, and keeping the temperature for 1-24 hours to obtain the potassium vanadium oxyfluoride phosphate.
The selection of the source of vanadium source reductant here is in accordance with the selection principle described above.
Potassium, sodium, vanadium, phosphorus and fluorine sources conventional in the art may be used in the present invention.
More preferably, the potassium salt is one or more of potassium fluoride, potassium hydroxide, potassium carbonate, potassium bicarbonate, potassium nitrate or potassium acetate.
More preferably, the sodium salt is one or more of sodium fluoride, sodium acetate, sodium oxalate, sodium citrate, sodium hydroxide, sodium carbonate or sodium bicarbonate.
More preferably, the vanadium source is one or more of vanadium acetylacetonate, vanadyl acetylacetonate, ammonium metavanadate, vanadium pentoxide or vanadium trioxide.
The solvent used for dissolving is different according to the solubility of the selected raw materials. Such as easily water-soluble substances, dissolved by water; such as a substance easily soluble in an organic solvent, is dissolved by an organic solvent (e.g., N-dimethylformamide, N-methylpyrrolidone, etc.).
More preferably, the phosphorus source is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphorus pentoxide or disodium hydrogen phosphate.
More preferably, the fluorine source is one or both of potassium fluoride and ammonium fluoride.
More preferably, the reducing agent is one or more of ketjen black, acetylene black, graphene, carbon nanotubes, citric acid, glucose, polydopamine or polyvinylpyrrolidone.
The application of the novel potassium ion battery positive electrode material potassium vanadium oxyfluorophosphate in the potassium ion battery is also within the protection scope of the invention.
And mixing the potassium vanadium oxyfluoride phosphate serving as a positive electrode material with a conductive agent and a binder (for example, mixing the potassium vanadium oxyfluoride phosphate and the binder in a mass ratio of 7:2:1 or 8:1: 1), coating the mixture on a current collector, and drying to obtain the potassium ion battery positive electrode.
Conductive agent and binder, and selecting the materials commonly used in the field.
Compared with the prior art, the invention has the following beneficial effects:
the method utilizes the oxygen element to replace the fluorine element, so as to change the crystal structure and the transmission characteristic, and the finally obtained potassium vanadium oxyfluoride phosphate has the advantages of high energy-high power density, stable structure and long cycle life, reduces the cost and is beneficial to industrial production.
Drawings
FIG. 1 is a typical K provided in example 13V2(PO4)2O2xF3-2x(0.005. ltoreq. x.ltoreq.1) in an X-ray diffraction pattern;
FIG. 2 provides K for example 13V2(PO4)2O2F is a charge-discharge curve under the current density of 0.1-5A/g;
FIG. 3 is K provided in example 13V2(PO4)2O2F is a multiplying power diagram under the current density of 0.1-5A/g;
FIG. 4 shows K provided in example 13V2(PO4)2O2F cycle performance plot at 100mA/g current density.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Example 1
The embodiment provides a novel potassium-ion battery anode material-potassium vanadium fluorophosphate K3V2(PO4)2O2F, the preparation method comprises the following steps:
dissolving 1mmol of sodium fluoride, 2mmol of sodium acetate and 2mmol of ammonium dihydrogen phosphate in 20mL of deionized water, and marking as a solution 1; 2mmol of vanadyl acetylacetonate was dissolved in N, N-dimethylformamide and labeled as solution 2. Slowly adding the solution 1 into the solution 2, reacting to generate coprecipitation suspension, placing the suspension in a hydrothermal kettle, and keeping the temperature at 180 ℃ for 16h to obtain a product Na3V2(PO4)2O2F。
Mixing the obtained Na3V2(PO4)2O2Preparing electrode slurry by using F, acetylene black and PVDF (NMP as solvent) in a ratio of 8:1:1, coating the electrode slurry on an aluminum foil, and drying to obtain Na3V2(PO4)2O2And F electrode plates. The electrode sheet was used as a positive electrode, potassium metal was used as a negative electrode, 0.8mol/L KPF6(EC: DEC ═ 1:1 Vol% was used as a solvent) was used as an electrolyte, and Whatman glass fiber was used as a battery separator, thereby assembling a potassium ion button battery.
The button cell is circulated for 5 circles under the current density of 100mA/g to obtain K3V2(PO4)2O2F。
Example 2
The embodiment provides a novel potassium-ion battery anode material-potassium vanadium fluorophosphate K3V2(PO4)2O2F, prepared essentially as in example 1. Except that 1mmol of sodium fluoride, 2mmol of sodium oxalate and 2mmol of ammonium dihydrogen phosphate were weighed and dissolved in 20ml of deionized water, and labeled as solution 1; 2mmol of vanadyl acetylacetonate was dissolved in N-methylpyrrolidone and labeled as solution 2.
Example 3
The embodiment provides a novel potassium-ion battery anode material-potassium vanadium fluorophosphate K3V2(PO4)2O2F, the preparation method comprises the following steps:
taking 1mmol of sodium fluoride, 2mmol of sodium acetate, 2mmol of ammonium dihydrogen phosphate and 2mmol of vanadyl acetylacetonate, adding a proper amount of absolute ethyl alcohol, ball-milling for 2 hours at 600rpm under a high-energy planetary ball mill, placing the mixture in a protective atmosphere, heating to 700 ℃, keeping the temperature for 6 hours, and finally cooling to room temperature to obtain a final product K3V2(PO4)2O2F。
Example 4
The embodiment provides a novel potassium-ion battery anode material-potassium vanadium fluorophosphate K3V2(PO4)2O2F, which was prepared substantially identically to example 3, except that the ball milling was carried out at 600rpm for 4h, the mixture was placed in a protective atmosphere, the temperature was raised to 800 ℃ and the temperature was maintained for 6 h.
Example 5
The embodiment provides a novel potassium-ion battery anode material-potassium vanadium fluorophosphate K3V2(PO4)2O0.01F2.99The preparation method comprises the following steps:
dissolving 1mmol of sodium fluoride, 2mmol of sodium acetate and 2mmol of ammonium dihydrogen phosphate in 20ml of deionized water, and marking as a solution 1; 0.01mmol vanadyl acetylacetonate and 1.99mmol vanadium acetylacetonate were dissolved in N, N-dimethylformamide and labeled as solution 2. Slowly adding the solution 1 into the solution 2, reacting to generate coprecipitation suspension, placing the suspension in a hydrothermal kettle, and keeping the temperature at 180 ℃ for 16h to obtain a product Na3V2(PO4)2O0.01F2.99。
Mixing the obtained Na3V2(PO4)2O0.01F2.99Mixing with acetylene black and PVDF (NMP as solvent) at a ratio of 8:1:1 to obtain electrode slurry, coating on aluminum foil, and oven drying to obtain Na3V2(PO4)2O0.01F2.99An electrode sheet. The electrode sheet is used as a positive electrode,potassium metal is used as a negative electrode, 0.8mol/L KPF6(EC: DEC ═ 1:1 Vol% is used as a solvent) is used as an electrolyte, and Whatman glass fiber is used as a battery diaphragm, so that the potassium ion button battery is assembled.
The button cell is circulated for 5 circles under the current density of 100mA/g to obtain K3V2(PO4)2O0.01F2.99。
Sample characterization and Performance testing
(1) Sample characterization
FIG. 1 is a typical K provided in example 13V2(PO4)2O2xF3-2x(0.005. ltoreq. x.ltoreq.1), wherein when X is a different value, only a slight change in the unit cell parameter c is observed in the crystal structure analysis, and only a small angular shift of the whole is observed in the X-ray diffraction pattern.
(2) Performance testing
FIG. 2 is a charge/discharge curve of the battery of example 1 at a current density of 0.1-5A/g, from which it can be seen that the first discharge capacity is up to 105mAh/g, and there are two high voltage plateaus of 4.0V and 3.2V.
FIG. 3 is a rate chart of the battery at a current density of 0.1-5A/g, which shows that the battery still has a capacity of 65mAh/g at a high current density of 2A/g. And under the current density of 100mA/g, after 100 cycles, the capacity retention rate of 97 percent still exists (as shown in figure 4).
Example 2 provides K3V2(PO4)2O2The electrochemical performance of F is approximately similar to that of example 1, and the F also has two high-voltage working platforms, and good multiplying power and cycling performance.
Therefore, the potassium vanadium oxyfluoride phosphate provided by the invention has the advantages of high energy-high power density, stable structure and long cycle life.
While the foregoing is directed to particular example embodiments of the present invention, numerous modifications and adaptations may be made by those skilled in the art without departing from the principles of the present invention. Rather, the scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. A novel potassium ion battery anode material of potassium vanadium oxyfluorophosphate is characterized in that the chemical formula of the potassium vanadium oxyfluorophosphate is K3V2(PO4)2O2xF3-2xWherein x is more than or equal to 0.005 and less than or equal to 1.
2. The novel potassium-ion battery positive electrode material potassium vanadium fluorophosphate according to claim 1, wherein x is 1.
3. The preparation method of the novel potassium-ion battery positive electrode material potassium vanadium fluorophosphate in any one of claims 1 to 2, which is characterized by comprising the following steps: mixing Na3V2(PO4)2O2xF3-2xCarrying out ion exchange with potassium ions to obtain the potassium vanadium oxyfluorophosphate; or uniformly mixing potassium salt, a vanadium source, a phosphorus source, a fluorine source and a reducing agent, heating to 400-800 ℃ in a protective atmosphere, and keeping the temperature for 1-24 hours to obtain the potassium vanadium oxyfluorophosphate; the vanadium source and the reducing agent are used in such amounts that K is3V2(PO4)2O2xF3-2xThe valence state of (c) is balanced.
4. The method according to claim 3, wherein the Na is3V2(PO4)2O2xF3-2xThe preparation method is characterized by comprising a hydrothermal method, a solid phase method, a sol-gel method, a spray drying method, an electrostatic spraying method or electrostatic spinning.
5. The method according to claim 4, wherein the Na is3V2(PO4)2O2xF3-2xPrepared by a hydrothermal method, wherein the hydrothermal method comprises the following steps:
s11: dissolving and mixing sodium salt, a vanadium source, a phosphorus source, a fluorine source and a carbon source to obtain a coprecipitated suspension;
s12: performing hydrothermal reaction on the suspension of S11 to obtain Na3V2(PO4)2O2xF3-2x。
6. The preparation method according to claim 3 or 5, wherein the potassium salt is one or more of potassium fluoride, potassium hydroxide, potassium carbonate, potassium bicarbonate, potassium nitrate or potassium acetate; the sodium salt is one or more of sodium fluoride, sodium acetate, sodium oxalate, sodium citrate, sodium hydroxide, sodium carbonate or sodium bicarbonate; the vanadium source is one or more of vanadium acetylacetonate, vanadyl acetylacetonate, ammonium metavanadate, vanadium pentoxide or vanadium trioxide; the phosphorus source is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphorus pentoxide or disodium hydrogen phosphate; the fluorine source is one or two of potassium fluoride or ammonium fluoride; the reducing agent is one or more of Ketjen black, acetylene black, graphene, carbon nanotubes, citric acid, glucose, polydopamine or polyvinylpyrrolidone.
7. The preparation method according to claim 5, wherein the temperature of the hydrothermal reaction is 30 to 200 ℃ and the time of the hydrothermal reaction is 5 to 120 hours.
8. The preparation method according to claim 5, characterized in that the hydrothermal reaction further comprises the steps of filtering and drying.
9. The preparation method according to claim 3, wherein the ion exchange process comprises: mixing Na3V2(PO4)2O2xF3-2xAs the anode, the metal potassium sheet is used as the cathode, and after the battery is assembled, the battery is circulated for a plurality of circles under certain current density until all sodium ions are replaced by potassium ions, and the potassium vanadium oxyfluoride phosphate is obtained;
or mixing Na3V2(PO4)2O2xF3-2xMixing with potassium salt in solvent, heating and refluxing, K+And Na+Ion exchange is carried out to obtain the potassium vanadium oxyfluoride phosphate.
10. The use of the novel potassium ion battery positive electrode material potassium vanadium fluorophosphate in potassium ion batteries as claimed in any one of claims 1 to 2.
CN202010537217.1A 2020-06-12 2020-06-12 Novel potassium ion battery positive electrode material potassium vanadium fluorophosphate and preparation method and application thereof Pending CN113800495A (en)

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CN113046768A (en) * 2021-03-15 2021-06-29 东北师范大学 Potassium vanadyl fluorophosphate, preparation method and application thereof, and potassium ion battery
CN115051026A (en) * 2022-07-04 2022-09-13 湖南大学 Novel potassium ion solid electrolyte material and preparation method and application thereof
CN115286049A (en) * 2022-07-26 2022-11-04 青岛大学 Preparation method of lithium-doped potassium nickel manganate material, positive electrode material and battery

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Application publication date: 20211217