CN115818719B - Double-ion doped positive electrode material, preparation method and battery - Google Patents
Double-ion doped positive electrode material, preparation method and battery Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 150000002500 ions Chemical class 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 239000010949 copper Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000446 fuel Substances 0.000 claims abstract description 12
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 11
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- 238000002156 mixing Methods 0.000 claims abstract description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 40
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 24
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 22
- 235000004279 alanine Nutrition 0.000 claims description 22
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical group [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 9
- 239000010406 cathode material Substances 0.000 claims description 8
- 230000009977 dual effect Effects 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000010405 anode material Substances 0.000 abstract description 12
- 238000005049 combustion synthesis Methods 0.000 abstract description 10
- 238000002485 combustion reaction Methods 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000011572 manganese Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 229910013553 LiNO Inorganic materials 0.000 description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- -1 mn (NO 3)2 Chemical compound 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
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- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
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- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
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- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The application discloses a double-ion doped positive electrode material, a preparation method and a battery, and relates to the technical field of battery materials. The preparation method of the double-ion doped positive electrode material comprises the following steps: dissolving manganese nitrate, a lithium source, a copper source and fuel in water, and stirring and mixing to obtain a mixed solution; heating and burning the mixed solution for 20-30 min, standing, and cooling to obtain a reactant; and grinding the reactant to obtain the double-ion doped anode material. The material is obtained through low-temperature combustion synthesis, has high combustion reaction speed, simple operation process and low cost, and is easy to realize industrial production. And the metal Cu and Li are used for double ion doping, so that the conductivity of the anode material can be obviously enhanced under the synergistic effect of double ions, and better structural stability is shown.
Description
Technical Field
The application relates to the field of battery materials, in particular to a double-ion doped positive electrode material, a preparation method and a battery.
Background
In recent years, along with the increasing shortage of energy sources and the aggravation of environmental protection problems, electrochemical energy storage technologies taking lithium ion batteries as a dominant material are widely applied to portable devices such as earphones, mobile phones, digital codes, tablet computers and the like, and large-scale devices such as electric automobiles, energy storage power stations and the like due to the characteristics of convenient use, high energy conversion efficiency, high energy density, high power density and the like. However, lithium ion batteries have poor safety and are prone to environmental pollution due to leakage. The use of zinc ion batteries as a safer, more environmentally friendly, more economical green energy source and aqueous electrolytes has led to the growing acceptance of aqueous secondary batteries as one of the important energy storage devices by the research community.
The aqueous zinc ion battery is nonflammable and uses a less toxic aqueous electrolyte than the lithium ion battery, thereby improving safety. The resistivity of metallic zinc is about 5.9 mu omega cm and remains stable in air and water. The oxidation-reduction potential of the zinc cathode in the water-based electrolyte is low (-0.76V), and zinc atoms lose two electrons in the electrochemical reaction process, so that more charges can be carried than single-electron lithium ions and the like, and the power density and the energy density of the battery are higher. Therefore, metallic zinc is currently considered to be an ideal negative electrode material for aqueous batteries.
In recent years, scientific researchers have developed a series of intensive researches on water-based zinc ion battery cathode materials, and currently, main zinc ion battery cathode materials comprise vanadium oxide, manganese oxide, molybdenum oxide, prussian blue derivatives and the like. Among them, manganese oxide has long been considered as a promising energy storage material due to its special advantages of low cost, abundant reserves, environmental friendliness, low toxicity, and polyvalent states (Mn 2+、Mn3+、Mn4+ and Mn 7+). Currently, manganese oxide (MnOx) applied to zinc ion batteries is generally prepared by a hydrothermal method, a coprecipitation method, a template method and the like. However, these methods have problems that the synthesis period is long, the synthesis steps are complicated, and mass production is impossible.
Disclosure of Invention
It is a primary object of the present application to provide a dual ion doped cathode material, a method of preparing the same, and a battery, which overcome, at least in part, one or more of the problems due to the limitations and disadvantages of the related art.
In order to achieve the purposes of the application, the application adopts the following technical scheme:
according to one aspect of the present application, there is provided a method for preparing a dual ion doped cathode material, comprising:
dissolving manganese nitrate, a lithium source, a copper source and fuel in water, and stirring and mixing to obtain a mixed solution;
Heating and burning the mixed solution for 20-30 min, standing, and cooling to obtain a reactant;
And grinding the reactant to obtain the double-ion doped anode material.
According to an embodiment of the application, the lithium source is selected from lithium nitrate and the copper source is selected from copper nitrate.
According to an embodiment of the application, the fuel is a mixture of alanine and ethanolamine.
According to one embodiment of the application, the molar ratio of the alanine to the ethanolamine to the manganese nitrate is 1.1-1.3:0.3-0.5:1.
According to one embodiment of the application, the copper source is used in an amount of 18-23% by mass of the manganese nitrate, and the lithium source is used in an amount of 0.2-0.7% by mass of the manganese nitrate.
According to an embodiment of the present application, the method further comprises post-treating the dual ion doped cathode material, the post-treating comprising: and soaking the double-ion doped anode material in dilute sulfuric acid or dilute nitric acid solution for 2-3 hours, and then sintering.
According to one embodiment of the application, in the post-treatment step, the sintering temperature is 600-800 ℃ and the sintering time is 1-2 hours.
According to one embodiment of the present application, the temperature of the mixed solution for heating and burning is 200-400 ℃.
According to another aspect of the present application, there is provided a dual ion doped cathode material prepared according to the preparation method as described in any one of the above.
According to yet another aspect of the present application, there is provided a zinc ion battery comprising:
The negative electrode is made of zinc metal;
A positive electrode comprising a dual ion doped positive electrode material as described above; and
An aqueous electrolyte.
In the embodiment of the application, manganese nitrate, a lithium source and a copper source are used as raw materials, a proper amount of fuel is added, and low-temperature combustion synthesis is carried out to obtain the bimetal ion doped Mn 3O4. The reaction is carried out in solution, so that the raw materials can be uniformly mixed at the atomic or molecular level, and the doping effect is provided. In addition, the low-temperature combustion method can release a large amount of energy and gas in the reaction process, has a dispersing effect on powder, and can prepare a product with high specific surface area. And the combustion reaction speed is high, the operation process is simple, the cost is low, and the industrial production is easy to realize.
In addition, double ion doping is carried out by metal Cu and Li, under the synergistic effect of double ions, the conductivity of the anode material can be obviously enhanced, the charge transfer capacity is improved, better structural stability is shown, structural damage in the charge and discharge process is prevented, and the overall performance of the zinc ion battery system is improved.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the application as claimed.
Drawings
The above and other features and advantages of the present application will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings.
FIG. 1 is an XRD pattern of a sample obtained in example 1 and comparative examples 1 to 3 of the present disclosure;
FIG. 2 is an SEM image of a sample obtained according to example 1 of the disclosure;
FIG. 3 is an SEM image of a sample obtained according to comparative example 1 of the present disclosure;
Fig. 4 is a graph comparing cycle performance of samples obtained in example 1 and comparative examples 1 to 3 of the present disclosure.
Detailed Description
Example embodiments will now be described more fully with reference to the accompanying drawings. However, the exemplary embodiments can be embodied in many forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the example embodiments to those skilled in the art. The same reference numerals in the drawings denote the same or similar structures, and thus detailed descriptions thereof will be omitted.
In this embodiment, the specific conditions are not specified in the examples, and the specific conditions are performed according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The following describes a specific description of the bipolar ion-doped positive electrode material, the production method, and the battery according to the present embodiment.
The embodiment of the application provides a preparation method of a double-ion doped anode material, which comprises the following steps:
Step S1, dissolving manganese nitrate (Mn (NO 3)2), a lithium source, a copper source and fuel in water, and stirring and mixing to obtain a mixed solution;
Step S2, heating and burning the mixed solution for 20-30 min, standing, and cooling to obtain a reactant;
and step S3, grinding the reactant to obtain the double-ion doped anode material.
Specifically, in one embodiment, in step S1, the lithium source is selected from lithium nitrate and the copper source is selected from copper nitrate. In the embodiment, two specific metal ions, namely Cu ions and Li ions, are selected to dope the positive electrode material, and the conductivity and the structural stability of the positive electrode material are improved through the synergistic effect of the Cu ions and the Li ions. Better cycling performance is obtained compared to single ion doping or other double ion doping.
Further, the stirring process is magnetic stirring for 15-30 min, for example, magnetic stirring for 15min, and the uniform mixing of the raw materials is ensured through magnetic stirring.
Further, the lithium source is selected from lithium nitrate (LiNO 3) and the copper source is selected from copper nitrate (Cu (NO 3)2).
Further, the fuel is a mixture of alanine and ethanolamine. Preferably, the molar ratio of the alanine to the ethanolamine is 1.1-1.3:0.3-0.5. The selection of the fuel has an important influence on the crystal structure of the anode material, and when alanine and ethanolamine with the molar ratio of 1.1-1.3:0.3-0.5 are selected as the fuel, the crystal growth is better, and the intensity of the characteristic peak is higher. And the obtained positive electrode material has better cycle performance.
Furthermore, the molar ratio of alanine to Mn (NO 3)2 is 1.1-1.3:1. By regulating the dosage of fuel and manganese nitrate, the smooth low-temperature combustion process is ensured.
Further, cu (NO 3)2 is used in an amount of Mn (18 to 23% by mass of NO 3)2), and LiNO 3 is used in an amount of Mn (0.2 to 0.7% by mass of NO 3)2), for example, cu (NO 3)2、LiNO3 is used in an amount of Mn (20% and 0.5% of NO 3)2, respectively).
In the embodiment, the doping amount of Cu ions is far higher than that of Li, and the doping is mainly carried out by regulating and controlling the dosage of Cu ions and micro lithium ions, so that Mn 3O4 is induced to generate lattice defects, the volume of a unit cell is expanded, the ion diffusion speed is greatly improved, and the cycle performance is improved.
Specifically, in one embodiment, in step S2, the temperature of the mixed solution is 200 to 400 ℃. The positive electrode material is obtained through low-temperature combustion synthesis.
Further, in step S2, after the combustion is completed, the mixture is allowed to stand for at least 30 minutes or longer, and the low-temperature combustion reactant is obtained after cooling.
Specifically, in one embodiment, in step S3, the resulting reactant is milled to yield crude Mn 3O4 having a particle size of less than 1 micron.
Specifically, the preparation method further comprises the following steps:
And S4, carrying out post-treatment on the double-ion doped anode material. Specifically, the post-processing includes: and soaking the double-ion doped anode material in dilute sulfuric acid or dilute nitric acid solution for 2-3 hours, and then sintering.
Preferably, the mass fraction of the dilute sulfuric acid or the dilute nitric acid solution is 2-6%. The soaking process is carried out at the temperature of 40-50 ℃ in an oil bath.
Further, in the step S4, the sintering temperature is 600-800 ℃ and the sintering time is 1-2 hours.
Soaking by dilute acid, and sintering to further refine the crystal grains of the crude Mn 3O4 obtained in the step S3, and forming a coarse structure on the surfaces of the crystal grains, so that the specific surface area of the particles is increased, and agglomeration is reduced.
The implementation method of the application also provides a double-ion doped anode material, which is prepared according to the preparation method.
The embodiment of the application also provides a zinc ion battery, which comprises a negative electrode, a positive electrode and an aqueous electrolyte, wherein the negative electrode is zinc metal; the positive electrode comprises the double ion doped positive electrode material.
The aqueous electrolyte may be an electrolyte component in the prior art, for example, the aqueous electrolyte contains zinc sulfate in an amount of 2 to 3 mol/L and/or manganese sulfate in an amount of 0.2 to 0.5 mol/L.
The features and capabilities of the present disclosure are described in further detail below in connection with the examples.
Example 1
The embodiment provides a double-ion doped positive electrode material, which is prepared according to the following steps:
(1) Alanine 1068 g, ethanolamine 244 g, mn (NO 3)2 179 g、Cu(NO3)2 35.8 g、LiNO3 0.9 g;
(2) Dissolving alanine, ethanolamine, mn (NO 3)2、Cu(NO3)2 and LiNO 3) in deionized water, and magnetically stirring for 20min to obtain a mixed solution.
(3) The mixed solution is subjected to low-temperature combustion synthesis reaction at the temperature of 250 ℃;
(4) After the reaction, standing for 45min, cooling, and grinding to obtain sample 1 (Mn 3O4 +Cu+Li).
Example 2
The embodiment provides a double-ion doped positive electrode material, which is prepared according to the following steps:
(1) Alanine 1157 g, ethanolamine 183 g, mn (NO 3)2 179 g、Cu(NO3)2 35.8 g、LiNO3 0.9 g;
(2) Dissolving alanine, ethanolamine, mn (NO 3)2、Cu(NO3)2 and LiNO 3) in deionized water, and magnetically stirring for 20min to obtain a mixed solution.
(3) The mixed solution is subjected to low-temperature combustion synthesis reaction at 200 ℃;
(4) After the reaction, standing for 45min, cooling, and grinding to obtain a sample 2.
The sample obtained a capacity retention of 96.3% for the zinc ion cell after 1000 cycles, tested (test method shown in example 1).
Example 3
The embodiment provides a double-ion doped positive electrode material, which is prepared according to the following steps:
(1) Alanine 1068 g, ethanolamine 244 g, mn (NO 3)2 179 g、Cu(NO3)2 35.8 g、LiNO3 0.9 g;
(2) Dissolving alanine, ethanolamine, mn (NO 3)2、Cu(NO3)2 and LiNO 3) in deionized water, and magnetically stirring for 20min to obtain a mixed solution.
(3) The mixed solution is subjected to low-temperature combustion synthesis reaction at the temperature of 250 ℃;
(4) And after the reaction is finished, standing for 45min, cooling, and grinding to obtain a ground substance.
(5) Immersing the ground material in a 4wt% dilute sulfuric acid solution, soaking for 2 hours at the temperature of 45 ℃ in an oil bath, filtering, and drying to obtain an acid treated material;
(6) The acid treated matter was placed in a muffle furnace and sintered at 650 ℃ for 2h to obtain sample 3.
Example 4
The embodiment provides a double-ion doped positive electrode material, which is prepared according to the following steps:
(1) Alanine 1312 g, mn (NO 3)2 179 g、Cu(NO3)2 35.8 g、LiNO3 0.9 g;
(2) Dissolving alanine, ethanolamine, mn (NO 3)2、Cu(NO3)2 and LiNO 3) in deionized water, and magnetically stirring for 20min to obtain a mixed solution.
(3) The mixed solution is subjected to low-temperature combustion synthesis reaction at the temperature of 250 ℃;
(4) After the reaction, standing for 45min, cooling, and grinding to obtain a sample 4.
Comparative example 1
This comparative example provides a positive electrode material prepared according to the following steps:
(1) Alanine 1068 g, ethanolamine 244 g, mn (NO 3)2 179 g;
(2) Dissolving alanine, ethanolamine and Mn (NO 3)2) in deionized water, and magnetically stirring for 20min to obtain a mixed solution.
(3) The mixed solution is subjected to low-temperature combustion synthesis reaction at the temperature of 250 ℃;
(4) After the reaction, the mixture was allowed to stand for 45 minutes, cooled and ground to obtain sample 5 (Mn 3O4).
Comparative example 2
This comparative example provides a positive electrode material prepared according to the following steps:
(1) Alanine 1068 g, ethanolamine 244 g, mn (NO 3)2 179 g、Co(NO3)2 35.8 g、LiNO3 0.9 g;
(2) Dissolving alanine, ethanolamine, mn (NO 3)2、Cu(NO3)2 and LiNO 3) in deionized water, and magnetically stirring for 20min to obtain a mixed solution.
(3) The mixed solution is subjected to low-temperature combustion synthesis reaction at the temperature of 250 ℃;
(4) After the reaction, standing for 45min, cooling, and grinding to obtain sample 6 (Mn 3O4 +Cu).
Comparative example 3
This comparative example provides a positive electrode material prepared according to the following steps:
(1) Alanine 1068 g, ethanolamine 244 g, mn (NO 3)2 179 g、Co(NO3)2 35.8 g、LiNO3 0.9 g;
(2) Dissolving alanine, ethanolamine, mn (NO 3)2、Cu(NO3)2 and LiNO 3) in deionized water, and magnetically stirring for 20min to obtain a mixed solution.
(3) The mixed solution is subjected to low-temperature combustion synthesis reaction at the temperature of 250 ℃;
(4) After the reaction, standing for 45min, cooling, and grinding to obtain sample 7 (Mn 3O4 +Co+Li).
Test example 1
XRD tests were performed on the samples obtained in example 1 and comparative examples 1 to 3, and the results are shown in FIG. 1. As can be seen from fig. 1, the phase of the positive electrode material is not changed after ion doping. As opposed to single ion doping or other double ion doping. The characteristic peak intensity of the sample of this embodiment is higher.
Test example 2
The samples obtained in example 1 and comparative example 1 were subjected to scanning electron microscopy, as shown in fig. 2, which is an SEM image of example 1, and as shown in fig. 3, which is an SEM image of comparative example 1. As can be seen from fig. 2 and 3, the positive electrode material obtained in the embodiment of the present disclosure has a smaller particle size, and the product morphology is uniform, so that a larger specific surface area can be formed, compared to the case where ion doping is not performed in the comparative document 1.
Test example 3
After 70 parts by weight of a positive electrode material (samples obtained in examples and comparative examples) and 20 parts by weight of a conductive agent (ketjen black) were mixed with 10 parts by weight of a binder (PTFE), the mixture was coated on a current collector of a suitable size, and dried in a vacuum drying oven to obtain a positive electrode sheet. The button half cell was assembled with a zinc sulfate aqueous solution having a concentration of 2.5 mol/L as an electrolyte, a zinc sheet as a counter electrode, and glass fiber as a separator, and the cycle performance was tested at a current density of 100mA g -1.
The test results are shown in fig. 4 and table 1.
TABLE 1
| Sample of | First charge-discharge efficiency% | Capacity retention rate of 100 cycles | Capacity retention rate of 500 cycles |
| Example 1 | 83.2% | 94.3% | 86.74% |
| Example 2 | 82.6% | 94.1% | 86.3% |
| Example 3 | 89.1% | 96.7% | 90.0% |
| Example 4 | 78.2% | 90.5% | 79.8% |
As can be seen from fig. 4 and table 1, in the embodiment of the present disclosure, by Cu and Li double ion doping, the product obtained has more excellent cycle performance than the comparative example. And the fuel consumption is adjusted and the secondary sintering is carried out, so that the structure of the anode material is thinned, and the performance of the material can be further improved.
In the description of the present specification, the terms "one embodiment," "some embodiments," "particular embodiments," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of an application embodiment. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The above is only a preferred embodiment of the application embodiment, and is not intended to limit the application embodiment, and various modifications and changes may be made to the application embodiment by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the embodiments of the application should be included in the protection scope of the embodiments of the application.
Claims (4)
1. The preparation method of the double-ion doped positive electrode material is characterized by comprising the following steps of:
Dissolving manganese nitrate, a lithium source, a copper source and fuel in water, and stirring and mixing to obtain a mixed solution; the fuel is a mixture of alanine and ethanolamine, and the molar ratio of the alanine to the ethanolamine to the manganese nitrate is 1.1-1.3:0.3-0.5:1; the consumption of the copper source is 18-23% of the mass of the manganese nitrate, and the consumption of the lithium source is 0.2-0.7% of the mass of the manganese nitrate;
Heating and burning the mixed solution for 20-30 min, standing, and cooling to obtain a reactant, wherein the temperature of heating and burning the mixed solution is 200-400 ℃;
grinding the reactant to obtain a ground product;
Post-treating the abrading article, the post-treating comprising: soaking the grinding material in dilute sulfuric acid or dilute nitric acid solution for 2-3 hours, and then sintering; wherein the mass fraction of the dilute sulfuric acid or the dilute nitric acid solution is 2-6%, and the soaking process is performed at the oil bath temperature of 40-50 ℃; the sintering temperature is 600-800 ℃, and the sintering time is 1-2 h.
2. The method of preparing a dual ion doped cathode material according to claim 1, wherein the lithium source is selected from lithium nitrate and the copper source is selected from copper nitrate.
3. A dual ion doped cathode material, characterized in that it is prepared according to the preparation method of any one of claims 1 to 2.
4. A zinc-ion battery, comprising:
The negative electrode is made of zinc metal;
A positive electrode comprising the dual ion doped positive electrode material of claim 3; an aqueous electrolyte.
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| CN113735174A (en) * | 2021-08-12 | 2021-12-03 | 郑州大学 | Aqueous zinc ion battery positive electrode material based on monovalent cation doped manganese-based compound and preparation method and application thereof |
| CN113782727A (en) * | 2021-09-13 | 2021-12-10 | 厦门理工学院 | Preparation method of zinc ion battery doped positive electrode material, zinc ion battery doped positive electrode material and zinc ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113735174A (en) * | 2021-08-12 | 2021-12-03 | 郑州大学 | Aqueous zinc ion battery positive electrode material based on monovalent cation doped manganese-based compound and preparation method and application thereof |
| CN113782727A (en) * | 2021-09-13 | 2021-12-10 | 厦门理工学院 | Preparation method of zinc ion battery doped positive electrode material, zinc ion battery doped positive electrode material and zinc ion battery |
Non-Patent Citations (1)
| Title |
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| Copper-doped manganese tetroxide composites with excellent electrochemical performance for aqueous zinc-ion batteries;Dong Li et al;《Journal of Electroanalytical Chemistry》;第888卷;第1-8页 * |
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