CN114628677A - Copper-doped potassium manganate electrode material, preparation method thereof and application thereof in potassium ion battery - Google Patents
Copper-doped potassium manganate electrode material, preparation method thereof and application thereof in potassium ion battery Download PDFInfo
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- 229910001414 potassium ion Inorganic materials 0.000 title claims abstract description 24
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000007772 electrode material Substances 0.000 title claims abstract description 20
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 29
- 230000014759 maintenance of location Effects 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 9
- 238000000498 ball milling Methods 0.000 claims description 9
- 239000007774 positive electrode material Substances 0.000 claims description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
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- 125000004122 cyclic group Chemical group 0.000 claims description 3
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- 230000005764 inhibitory process Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 39
- 239000011572 manganese Substances 0.000 description 29
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 20
- 239000012071 phase Substances 0.000 description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 13
- 229910052748 manganese Inorganic materials 0.000 description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052700 potassium Inorganic materials 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000002238 attenuated effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
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- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910021135 KPF6 Inorganic materials 0.000 description 1
- 229910016447 Mn0.9Cu0.1O2 Inorganic materials 0.000 description 1
- 101000774651 Naja atra Zinc metalloproteinase-disintegrin-like kaouthiagin-like Proteins 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
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- 230000001788 irregular Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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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- 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
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Abstract
The invention relates to a copper-doped potassium manganate electrode material, a preparation method thereof and application thereof in a potassium ion battery, belonging to the technical field of potassium ion battery materials. The KCMO after copper doping is a P3 phase, and the generation of an orthorhombic mixed phase is inhibited by the copper doping. The electrochemical performance of the copper-doped KCMO is greatly improved. The discharge specific capacity is 106.5mAh g in a wider voltage range (1.5-3.9V) at a multiplying power of 0.5C‑1And when the circulation is carried out under the condition of high multiplying power of 5C, the capacity of the first circle reaches 88.8mAh g‑1The retention ratio of discharge capacity after 200 cycles was 65.1%. When the upper limit voltage is increased to 4.2V, the specific discharge capacity of the material is increased to 117mAh g‑1And can still stably circulate for a certain number of circles, thus widening the electrochemical window of the material. Capacity, cyclicity of KCMOThe multiplying power performance and the electrochemical window are greatly improved.
Description
Technical Field
The invention relates to a copper-doped potassium manganate electrode material, a preparation method thereof and application thereof in a potassium ion battery, belonging to the technical field of potassium ion battery materials.
Background
In recent years, people gradually realize the importance of environmental protection and sustainable development, and renewable energy sources such as wind energy and solar energy are developed and utilized unprecedentedly. Secondary batteries are used as an excellent energy storage device often in combination with these intermittent renewable energy sources to achieve efficient use of energy, and thus demand for secondary batteries is increasing. In terms of performance, the current mature lithium ion battery technology is very suitable for being applied to a large-scale energy storage system, but the development of the lithium ion battery is limited by the limited lithium resource and high cost. Emerging potassium ion batteries are widely concerned by researchers due to abundant potassium resource reserves, low cost and similar physicochemical properties of potassium and lithium, and are considered to meet the requirements of large-scale energy storage systems. In addition, the standard oxidation-reduction potential (-2.94V vs. SHE) of potassium is closer to the standard oxidation-reduction potential (-3.04V vs. SHE) of lithium than the standard oxidation-reduction potential (-2.73V vs. SHE) of sodium, and therefore, the potassium ion battery has certain advantages in terms of voltage output. And the Stokes radius of the solvation of potassium ions in the electrolyte is smaller than that of lithium ions and sodium ions, and the ion conductivity is higher, so that the potassium ion battery can realize better rate performance. Unlike sodium ion batteries which are limited in that the graphite cathode cannot be inserted and extracted with sodium ions, graphite has been proved to be applicable to potassium ion batteries, which lays a good foundation for the practical application of potassium ion batteries. Although more and more researchers are involved in the research of the potassium ion battery material, the potassium ion battery anode material with high energy density and excellent cycle performance still needs to be further developed.
The manganese-based layered oxide is considered to be a positive electrode material with a good prospect due to rich manganese resources, no toxicity, environmental protection and low cost. In addition, manganese is rich in valence state (from Mn)2+To Mn4+) Can be flexibleThe voltage range of the battery is adjusted, and larger battery capacity is provided. K0.3MnO2And K0.5MnO2The related research proves that the manganese-based layered oxide has the activity of storing potassium, the potassium content in the two original materials is lower, compared with other layered materials such as cobalt-based materials, the chromium-based layered material can basically contain more than 0.6 potassium, and the two manganese-based materials have the problems of excessive phase change, fast capacity attenuation, poor rate capability and the like in the charging and discharging processes.
Considering that the radius of potassium ion is large, the kinetics of chemical reaction is slow in the ion deintercalation process, and its layered oxide is sensitive to moisture in the air. Therefore, it is difficult to deduce how to prepare a suitable electrode material and whether the electrode material can exhibit corresponding charge and discharge performance when applied to a battery from the prior art, and therefore, the development of a corresponding electrode material for a potassium ion battery is required.
Disclosure of Invention
The first technical problem to be solved by the invention is as follows: k in the prior art0.3MnO2And K0.5MnO2The capacity of the material is attenuated quickly in the charging and discharging process, the multiplying power performance is not good, the invention adopts a simple solid-phase sintering method and adopts Mn2O3The manganese-based layered oxide material is synthesized as a manganese source, and is P3 type K doped with a small amount of copper element0.6Cu0.1Mn0.9O2(abbreviated as KCMO). The doping of a small amount of copper effectively improves the electrochemical performance of the material and enables the electrode material to perform relatively stable electrochemical cycling under a wider voltage range.
The second technical problem to be solved by the invention is: in the process of preparing a p 3-phase manganese-based layered oxide powder sample by solid-phase sintering, an orthorhombic mixed peak can be generated in the obtained material, so that the purity of the material is not high; in the present invention, the doping of CuO can suppress the formation of an orthorhombic impurity phase, thereby obtaining a P3 phase material. The powder solid obtained by sintering does not generate a foreign peak, and generation of an orthorhombic foreign phase is suppressed.
The third technical problem to be solved by the invention is: when sintering treatment is carried out, when the material is directly taken out after being cooled, the electrochemical performance of the material is poor. The invention discovers that the problem is caused by the fact that the interlayer spacing of the potassium electric anode laminar material is large, and water intercalation is caused by the pollution of water in the air; this patent is through when cooling to specific temperature, with the sample shift continue the cooling to inert atmosphere in, has avoided the emergence of this problem.
In a first aspect of the present invention, there is provided:
a copper-doped potassium manganate electrode material with a structural formula of K0.6Cu0.1Mn0.9O2(ii) a And the crystal geometry is hexagonal and does not contain orthorhombic crystals.
In a second aspect of the present invention, there is provided:
the preparation method of the copper-doped potassium manganate electrode material comprises the following steps:
and step 2, pressing the powder subjected to ball milling, and sintering to obtain the electrode material.
In one embodiment, in step 1, K2CO3In an excess of 5% with respect to the stoichiometric ratio.
In one embodiment, in the step 1, the rotation speed of the ball milling process is 200 and 400rpm, and the ball milling time is 2-8 h.
In one embodiment, in the step 2, the sintering process is 700-900 ℃ for 10-20 h.
In one embodiment, the sample is protected from moist air after furnace cooling to 200 ℃ after sintering is complete.
In a third aspect of the present invention, there is provided:
the copper-doped potassium manganate electrode material is applied to a potassium ion battery.
In one embodiment, in the application, the electrode material is used as a positive electrode material, and the positive electrode slurry used is prepared by mixing the positive electrode material, acetylene black and PVDF in a weight ratio of 7: 2: 1 are mixed to obtain the product.
In one embodiment, the electrolyte in a potassium ion battery has a KPF of 0.8M6Dissolved in Ethylene Carbonate (EC) and diethyl carbonate (DEC), where EC: volume ratio of DEC 1: 1.
in one embodiment, the copper-doped potassium manganate electrode material is used for improving the first-turn charging specific capacity, the discharging specific capacity or the specific capacity retention rate in cyclic charging and discharging of a potassium ion battery.
In a fourth aspect of the present invention, there is provided:
use of doped copper in inhibition of sintering for preparing P3 type K0.6Cu0.1Mn0.9O2The use for the generation of orthorhombic heterophases.
Advantageous effects
The invention successfully synthesizes the P3 type manganese-based layered material K with the potassium content of 0.6 by adopting a solid-phase sintering process0.6MnO2(KMO for short) and adopts the same solid phase method to realize copper element doping, thus synthesizing P3 type K0.6Cu0.1Mn0.9O2(abbreviated as KCMO). The electrochemical performance of KMO and KCMO as positive electrode materials of the potassium ion battery are compared and analyzed by X-ray diffraction (XRD) and Scanning Electron Microscope (SEM).
The KMO has a P3 phase as the main phase of the structure, but contains a small amount of K belonging to orthorhombic systemxMnO2The first ring of the impurity has larger specific discharge capacity, and the capacity is 98.6mAh g under the voltage range of 1.5-3.8V with 0.2C multiplying power-1However, the cycle performance is not satisfactory, the discharge capacity retention rate after 50 cycles is only 16.1%, and the electrochemical performance needs to be further improved.
2. The copper-doped KCMO is also in a P3 phase, and the copper doping does not change the main crystal structure of the material and inhibits the generation of an orthorhombic mixed phase. The electrochemical performance of the copper-doped KCMO is greatly improved. By 0The discharge specific capacity of 5C rate in a wider voltage range (1.5-3.9V) is 106.5mAh g-1And when the circulation is carried out under the condition of high multiplying power of 5C, the capacity of the first circle reaches 88.8mAh g-1The retention ratio of discharge capacity after 200 cycles was 65.1%. And when the upper limit voltage is increased to 4.2V, the specific discharge capacity of the material is increased to 117mAh g-1And can still stably circulate for a certain number of circles, thus widening the electrochemical window of the material. Compared with KMO, the KCMO has great improvement in the aspects of capacity, cycle performance, rate capability and electrochemical window.
Drawings
FIG. 1 shows K prepared in example 10.6Mn0.9Cu0.1O2X-ray diffraction pattern of the powder sample.
FIG. 2 shows K prepared in comparative example 10.6MnO2A sample characterization map wherein region (a) is K0.6MnO2An X-ray diffraction pattern of the powder sample; (b) region is K0.6MnO2SEM image of powder sample.
FIG. 3 is a plot of KMO at 0.2C magnification across a voltage range of 1.5-3.8V (a) electrochemical curve; (b) and (4) a cycle performance graph.
FIG. 4 is a KCMO electrochemical performance characterization, wherein (a) region is an electrochemical curve with a voltage range of 1.5-3.9V, and (b) region is an electrochemical curve with a magnification of 0.5C with a voltage range of 1.5-4.2V.
FIG. 5 is a KCMO electrochemical performance characterization, wherein (a) is a cycle performance graph with a voltage range of 1.5-3.9V in the area, and (b) is a cycle performance graph with a magnification of 0.5C in the voltage range of 1.5-4.2V in the area.
FIG. 6 is a plot of the differential specific capacity of KCMO, where (a) is in the voltage range of 1.5-3.9V and (b) is in the voltage range of 1.5-4.2V.
FIG. 7 is a plot of charge and discharge performance of a KCMO material, wherein the electrochemical profile of region (a) at 0.5C rate; (b) the area is a rate performance graph of KCMO; (c) the region is a plot of the cycling performance of KCMO at 5C magnification.
FIG. 8 shows P3 form K prepared in comparative example 20.6Cu0.2Mn0.8O2Charge and discharge performance ofLine, wherein (a) zone is electrochemical plot at 0.5C rate; (b) the area is a rate performance graph; (c) the region is the cycle performance plot at 5C magnification.
FIG. 9 shows P3 form K prepared in comparative example 20.6Cu0.2Mn0.8O2The area (a) is a cyclic performance graph at 0.5C magnification, and the area (b) is a cyclic voltammogram.
Detailed Description
Example 1 copper-doped layered manganese-based cathode material P3 type K0.6Cu0.1Mn0.9O2Preparation and characterization of
P3 type K0.6Cu0.1Mn0.9O2Synthesized by a simple solid-phase sintering method. Firstly, weighing raw materials according to a stoichiometric ratio: k2CO3、Mn2O3And CuO, K2CO3(5% excess) was put into a ball mill and ball-milled at 300rpm for 5 hours. Taking out, pressing into a circular sheet with the diameter of 19mm by a tablet press, putting the circular sheet into an alumina crucible, feeding the circular sheet into a muffle furnace, and sintering for 15 hours at 800 ℃ in air. Finally, after cooling to 200 ℃ along with the furnace, the crucible and the wafer are sent into a glove box (to prevent the sample from contacting humid air), and the wafer is ground into powder for later use.
Comparative example 1 layered manganese-based cathode material P3 type K0.6MnO2Preparation of (2)
P3 type K0.6MnO2Synthesized by a simple solid-phase sintering method. Firstly, weighing raw materials according to a stoichiometric ratio: k2CO3(excess 5%) and Mn2O3And putting the mixture into a ball mill to perform ball milling for 5 hours at the rotating speed of 300 rpm. Taking out, pressing into a circular sheet with the diameter of 19mm by a tablet press, putting the circular sheet into an alumina crucible, feeding the circular sheet into a muffle furnace, and sintering for 15 hours at 800 ℃ in air. Finally, after cooling to 200 ℃ along with the furnace, the crucible and the wafer are sent into a glove box (to prevent the sample from contacting humid air), and the wafer is ground into powder for later use.
Comparative example 2 copper-doped layered manganese-based positive electrode material P3 type K0.6Cu0.2Mn0.8O2Preparation of
P3 type K0.6Cu0.2Mn0.8O2Synthesized by a simple solid-phase sintering method. Firstly, weighing raw materials according to a stoichiometric ratio: k2CO3、Mn2O3And CuO, K2CO3(5% excess) was put into a ball mill and ball-milled at 300rpm for 5 hours. Taking out, pressing into a wafer with the diameter of 19mm by a tablet press, putting into an alumina crucible, feeding into a muffle furnace, and sintering in the air at 800 ℃ for 15 hours. Finally, after cooling to 200 ℃ along with the furnace, the crucible and the wafer are sent into a glove box (to prevent the sample from contacting humid air), and the wafer is ground into powder for later use.
Comparative example 3
The difference from example 1 is that: the manganese source adopted in the preparation process is MnO2And the remaining parameters are the same.
Characterization of materials
K prepared in comparative example 10.6MnO2The X-ray diffraction pattern of the powder sample is shown as the area (a) of fig. 2, and the SEM image is shown as the area (b) of fig. 2; the Kapton film was used to seal the sample during XRD testing so a background between 12 deg. -30 deg. was associated with the Kapton film. From the XRD results, it can be known that synthesized K0.6MnO2The diffraction peak of the powder sample can be approximately equal to P3 phase KxMnO2The characteristic peaks of (A) are matched, and a small amount of mixed peaks exist, belonging to K of an orthorhombic systemxMnO2(space group cmcm). Thus synthesized K0.6MnO2The main phase is P3 phase, and the stacking sequence of oxygen is ABBCCA. The SEM picture shows that K is0.6MnO2The particles of (2) are irregular in shape, the diameter of the particles is between 1 and 2 mu m, and the phenomenon of particle agglomeration and agglomeration occurs.
P3 form K prepared as described in example 1 above0.6Cu0.1Mn0.9O2The X-ray diffraction pattern of the material is shown in figure 1. From the XRD results in the figure, it can be seen that the background between 12 deg. -30 deg. is associated with the Kapton film used to seal the powder, and that the synthesized K is0.6Cu0.1Mn0.9O2The diffraction peaks of the powder samples were substantially matched to the characteristic peaks of the P3 phase, with no unwanted hetero-peaks and no K-like peaks0.6MnO2Orthorhombic K can be generated in the synthesis processxMnO2The miscellaneous phase of (1). Thus synthesized K0.6Cu0.1Mn0.9O2Pure phase P3, unit cell parameters:
is in a hexagonal system. The doping of a small amount of copper does not change the crystal structure of the material and inhibits the generation of orthorhombic mixed phases to a certain extent.
Potassium ion battery assembly and testing
The assembled battery is a button battery, and the whole assembling process is carried out in a glove box in an argon atmosphere. Firstly, mixing a positive electrode material, acetylene black and PVDF according to a ratio of 7: 2: 1, uniformly mixing, adding a proper amount of solvent NMP to form slurry, and uniformly coating the slurry on an aluminum foil. And after drying, a wafer with the diameter of 12mm is carved by a carving machine to be used as the anode of the battery. A glass fiber membrane is used herein as the separator. The electrolyte used was 0.8M KPF6Dissolved in Ethylene Carbonate (EC) and diethyl carbonate (DEC), where EC: volume ratio of DEC 1: 1, the negative electrode uses a disk of potassium metal with a diameter of 12 mm. After the cells were assembled in a certain order, the glovebox was taken out and left to stand for 8 hours for electrochemical tests. 1C-100 mA g-1。
Potassium storage property of anode material
Electrochemical tests were performed on half cells with KMO as the positive electrode. As shown in the region (a) of FIG. 3, the first charge specific capacity of KMO was 49.2mAh g when the battery was charged and discharged at a rate of 0.2C in a voltage range of 1.5 to 3.8V-1Specific discharge capacity of 98.6mAh g-1. However, the capacity of KMO is quickly attenuated, and the capacity is attenuated to 62.2mAh g after only 3 cycles of circulation-1. The region (b) of fig. 3 also exhibited poor cycling performance in KMO, and the discharge capacity retention rate was only 16.1% after 50 cycles at 0.2C rate. These results all indicate that the undoped KMO material has poor structural stability during the re-electrochemical process, resulting in rapid capacity fade.
For KCMO material after copper dopingElectrochemical tests were performed. As shown in the region (a) of FIG. 4, the battery was charged and discharged at a rate of 0.5C over a wider voltage range of 1.5-3.9V than KMO, and the first-cycle charging specific capacity of KCMO was 49.9mAh g-1Discharge specific capacity of 106.5mAh g-1. And after 50 cycles, the capacity is still maintained at 78.7mAh g-1(region (a) of FIG. 5). Under the same current density, the upper limit cut-off voltage is improved by trying to change the voltage range to 1.5-4.2V, the upper limit cut-off voltage is improved, the voltage slope curve of more than 3.9V is prolonged, and the first-loop charging specific capacity of the KCMO is improved to 74mAh g-1The specific discharge capacity is improved to 117mAh g-1The electrochemical curve is shown in the region (b) of FIG. 4. After 50 cycles of charge and discharge, the capacity is reduced to 64.7mAh g-1(region (b) of FIG. 5). Compared with the electrochemical performance with the upper limit cut-off voltage of 3.9V, the initial specific discharge capacity with the cut-off voltage of 4.2V is improved, but certain cycle stability of the material is sacrificed. This also indicates that the material structure becomes unstable at high voltage, affecting the cycle performance of the battery.
As shown in FIG. 6, the dQ/dV curve obtained after the differential processing is performed on the first circle of electrochemical curve of KCMO in different voltage ranges shows that in the voltage range of 1.5-3.9V, the oxidation peaks and the reduction peaks of the material can be in one-to-one correspondence, so that good reversibility is embodied, and the cycle performance of KCMO in the voltage range is better. However, under a wider voltage range of 1.5-4.2V, a tiny oxidation peak near 4.19V does not correspond to the oxidation peak in the discharge process, which proves that the material structure is subjected to irreversible structural change under high voltage, and the subsequent electrochemical capacity attenuation is influenced. However, compared with the electrochemical performance that the discharge capacity retention rate is only 16.1% after 50 circles of KMO within 1.5-3.8V, the cycle performance of KCMO under high voltage (1.5-4.2V) is still considerable. In terms of comprehensive performance, 3.9V is taken as the upper limit cut-off voltage of the battery, so that the subsequent research is facilitated. As shown in the region (b) of FIG. 7, the KCMO rate performance is also very good, and the capacities at 0.1C, 0.5C, 1C, 2C, 5C, and 10C are 116.6mAh g respectively-1，94.3mAh g-1，84.4mAh g-1，74mAh g-1，53.2mAh g-1，36.1mAh g-1When the multiplying power is restored to 0.1C, the capacity is still 100.3mAh g-1The retention ratio with respect to the initial capacity was 86.1%. And when the circulation is carried out under the condition of high multiplying power of 5C, the capacity of the first circle reaches 88.8mAh g-1The discharge capacity retention rate after 200 cycles was as high as 65.1% (region (c) of fig. 7).
In addition, K0.6Cu0.1Mn0.9O2The addition of Cu in the material also has a large influence on the properties of the final material, such as K prepared in comparative example 20.6Cu0.2Mn0.8O2The electrochemical performance of the material is respectively shown in fig. 8 and fig. 9, and it can be seen from the figure that the discharge capacity retention rate is 57.9% after 200 cycles are completed when the cycle is performed at 5C; the discharge capacity retention after 50 cycles at 0.5C cycling was about 72.8%, which is significantly lower than the KCMO material prepared in example 1.
In addition, after the material prepared in comparative example 4 was assembled into a battery in the same manner, the discharge capacity retention rate was 43.8% after completing 200 cycles at 5C cycles; the discharge capacity retention after 50 cycles at 0.5C was about 61.2% lower than that of the KCMO material prepared in example 1.
These results all show that copper doping effectively improves the problem of KMO structural instability, and enables the KCMO to be optimally improved in capacity, cycle performance and electrochemical window.
Claims (10)
1. The copper-doped potassium manganate electrode material is characterized in that the structural formula is K0.6Cu0.1Mn0.9O2。
2. The preparation method of the copper-doped potassium manganate electrode material of claim 1, characterized by comprising the following steps: step 1, adding K according to stoichiometric ratio2CO3、Mn2O3Mixing with CuO and then ball-milling; and step 2, pressing the powder subjected to ball milling, and sintering to obtain the electrode material.
3. The method according to claim 2, wherein in step 1, K is the same as K2CO3In an amount of 5% excess with respect to the stoichiometric ratio.
4. The method as claimed in claim 2, wherein the rotation speed of the ball milling process in step 1 is 200-400rpm, and the ball milling time is 2-8 h.
5. The method as claimed in claim 2, wherein the step 2 is sintering at 900 ℃ for 10-20h at 700-.
6. The use of the copper-doped potassium manganate electrode material of claim 1 in potassium ion batteries.
7. The use according to claim 6, wherein in one embodiment, the electrode material is used as a positive electrode material, and a positive electrode slurry is prepared from the positive electrode material, acetylene black and PVDF in a weight ratio of 7: 2: 1 are mixed to obtain the product.
8. Use according to claim 6, wherein, in one embodiment, the electrolyte in a potassium ion battery has a KPF of 0.8M6Dissolved in Ethylene Carbonate (EC) and diethyl carbonate (DEC), where EC: volume ratio of DEC 1: 1.
9. the use according to claim 6, wherein in one embodiment, the copper-doped potassium manganate electrode material is used for improving the first-turn specific charge capacity, the first-turn specific discharge capacity or the specific capacity retention rate in cyclic charge and discharge of a potassium ion battery.
10. Use of doped copper in inhibition of sintering for preparing P3 type K0.6Cu0.1Mn0.9O2The use for the generation of orthorhombic heterophases.
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| CN115872462A (en) * | 2023-01-04 | 2023-03-31 | 中国地质大学（北京） | Preparation method of high-entropy oxide positive electrode material of potassium ion battery |
| CN116081694A (en) * | 2022-12-01 | 2023-05-09 | 北京科技大学 | Preparation method of lithium doped manganese-based layered oxide for positive electrode material of potassium ion battery |
| CN117334892A (en) * | 2023-09-07 | 2024-01-02 | 南京大学 | Manganese-based layered high-entropy oxide positive electrode material and preparation method thereof |
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