CN113422048A - Preparation method and application of novel water-based zinc ion battery positive electrode material - Google Patents
Preparation method and application of novel water-based zinc ion battery positive electrode material Download PDFInfo
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- CN113422048A CN113422048A CN202110695682.2A CN202110695682A CN113422048A CN 113422048 A CN113422048 A CN 113422048A CN 202110695682 A CN202110695682 A CN 202110695682A CN 113422048 A CN113422048 A CN 113422048A
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000007774 positive electrode material Substances 0.000 title claims description 22
- 239000000463 material Substances 0.000 claims abstract description 41
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 239000010405 anode material Substances 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 15
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 13
- 229930006000 Sucrose Natural products 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 150000002696 manganese Chemical class 0.000 claims abstract description 11
- 150000003751 zinc Chemical class 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000007605 air drying Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 230000001007 puffing effect Effects 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000003760 magnetic stirring Methods 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims description 17
- 239000005720 sucrose Substances 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000006258 conductive agent Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000011686 zinc sulphate Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 230000002441 reversible effect Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 18
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229960004793 sucrose Drugs 0.000 abstract 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 14
- 238000004146 energy storage Methods 0.000 description 10
- 239000011572 manganese Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RTHIDQYVBYGINB-UHFFFAOYSA-N zinc dinitrate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O RTHIDQYVBYGINB-UHFFFAOYSA-N 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
- H01M4/58—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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method and application of a novel water system zinc ion battery anode material, which comprises the steps of adding zinc salt, manganese salt and cane sugar into a solvent for uniform mixing, and carrying out magnetic stirring under the condition of water bath to form sol; transferring the obtained sol into a forced air drying box for puffing to obtain a sintering precursor; sintering the fluffy precursor in the atmosphere; cooling and grinding to obtain ZnMnO used as the anode material of the zinc ion battery3. The method has the advantages of wide material source, low raw material price, high product purity, energy and time conservation, high yield, and capability of meeting the requirements of low cost, green and environmental protection of the anode material of the water-system zinc-ion battery; and ZnMnO prepared3The material is applied to the anode material of the water system zinc ion battery, and has good initial specific capacity, excellent rate capability and cycleAnd (4) stability.
Description
Technical Field
The invention belongs to the technical field of chemical power sources, and particularly relates to a preparation method and application of a novel water-based zinc ion battery anode material.
Background
With the increasing environmental pollution and the consumption of fossil fuels, people are accelerating the pace of seeking new green energy. Some renewable clean energy sources, such as wind energy, solar energy, tidal energy and the like, are expected to replace traditional fossil energy sources, but the renewable clean energy sources also have the defects of uneven distribution, incapability of being used at any time and the like. Therefore, it is necessary to combine with some energy storage devices to effectively utilize the energy. The current energy storage modes mainly comprise mechanical energy storage, electrochemical energy storage, thermal energy storage, electrical energy storage and chemical energy storage. Compared with other energy storage modes, the electrochemical energy storage has the advantages of high conversion efficiency, flexible application, less investment and the like, and meets the requirement of energy development.
At present, lead-acid batteries, nickel-metal hydride batteries and lithium ion batteries are developed into relatively mature electrochemical energy storage modes. Among them, the lithium ion battery has advantages of high energy density, long cycle life, high working voltage, no memory effect, etc., and is widely used and favored. Although lithium ion batteries have many advantages, the storage capacity of lithium resources is limited and unevenly distributed, the price of lithium is gradually increased in recent years, and organic electrolytes used in lithium ion batteries have potential safety hazards, so that the application of lithium ion batteries in large-scale energy storage devices is limited. In order to find a suitable energy storage alternative technology, sodium ion batteries and potassium ion batteries are researched and developed correspondingly, but the raw materials of the batteries are high in price, and the assembly conditions of the batteries are strict (under the anhydrous and oxygen-free conditions), so that the cost of the batteries is high.
Recently, rechargeable aqueous ion batteries (such as magnesium, aluminum, zinc, etc.) have been receiving increasing attention due to their advantages of low cost, relative safety, environmental friendliness, etc. And the water system ion battery adopts the aqueous electrolyte, and the ion conductivity of the aqueous electrolyte is 2-3 orders of magnitude higher than that of the organic electrolyte, so that the aqueous electrolyte has higher multiplying power capability and can meet further practical application.
In many water-based ion batteries, zinc metal is abundant in resources, low in price, environment-friendly, and theoretical in capacity and volumeThe method has the advantages of high capacity, relative stability in aqueous solution and the like, and is widely researched. The water system zinc ion battery which is low in price, rich in materials and relatively safe also meets the requirements of a large-scale energy storage system. Based on the above advantages, in recent years, many researchers have made a lot of work on the search of aqueous zinc-ion batteries, and research on aqueous zinc-ion batteries has been rapidly advanced. At present, the research on zinc ion batteries mainly focuses on several aspects of positive electrode materials, negative electrode materials, separators and electrolytes, wherein the positive electrode materials are not only the key for determining the performance of the batteries, but also the key for preventing the practical application of the zinc ion batteries. Some monometallic manganese-based oxides, e.g. (MnO )2，Mn2O3，Mn3O4) Has been studied in large quantities as a positive electrode material for aqueous zinc-ion batteries.
However, for the single metal oxide, there are also problems that the conductivity is low, and that dissolution of manganese and structural collapse occur during charge and discharge, resulting in poor cycle stability thereof. Therefore, the search for a suitable novel water-based zinc ion cathode material is still a serious challenge, and the development of a novel cathode material with long service life, high specific capacity, high cycle stability, high safety, simple preparation process and environmental protection is the central importance of the development of the current water-based zinc ion battery.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.
Therefore, an object of the present invention is to provide a novel positive electrode material for aqueous zinc-ion batteries, which overcomes the drawbacks of the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of a novel water system zinc ion battery anode material is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
adding zinc salt, manganese salt and sucrose into a solvent, uniformly mixing, and performing magnetic stirring under the condition of water bath to form sol;
transferring the obtained sol into a forced air drying box for puffing to obtain a sintering precursor;
sintering the fluffy precursor in the atmosphere;
cooling and grinding to obtain ZnMnO used as the anode material of the zinc ion battery3。
As a preferable embodiment of the method for preparing the novel aqueous zinc-ion battery positive electrode material of the present invention, the method comprises: the zinc salt comprises any one of zinc nitrate heptahydrate, zinc sulfate and zinc chloride; the manganese salt comprises any one of manganese nitrate and manganese sulfate; the solvent comprises deionized water.
As a preferable embodiment of the method for preparing the novel aqueous zinc-ion battery positive electrode material of the present invention, the method comprises: adding zinc salt, manganese salt and sucrose into a solvent, and uniformly mixing, wherein the molar ratio of the zinc salt to the manganese salt is 1:1, and the molar ratio of the mixed salt of the zinc salt and the manganese salt to the sucrose is 1: 3.
As a preferable embodiment of the method for preparing the novel aqueous zinc-ion battery positive electrode material of the present invention, the method comprises: the puffing is carried out for 3 hours at the temperature of 120-180 ℃; and sintering the fluffy precursor in the atmosphere, wherein the temperature rise rate of the sintering is 1-20 ℃/min, the sintering temperature is 500-700 ℃, and the sintering time is 1-5 h.
As a preferable embodiment of the method for preparing the novel aqueous zinc-ion battery positive electrode material of the present invention, the method comprises: the puffing temperature is 140 ℃, and the calcining temperature is 600 ℃.
As a preferable embodiment of the method for preparing the novel aqueous zinc-ion battery positive electrode material of the present invention, the method comprises: the atmosphere is air or oxygen.
The product obtained by the preparation method of the novel water-based zinc ion battery positive electrode material provided by the invention comprises the following steps: the use of said composition, comprising,
ZnMnO is added3Uniformly mixing the material with a conductive agent and a binder, coating the mixture on a titanium foil, and drying the titanium foil in a drying oven at the temperature of 80 ℃ for 12 hours to obtain the novel water-based zinc ion battery positive pole piece; wherein,
the conductive agent comprises acetylene black;
the binder comprises polyvinylidene fluoride;
ZnMnO3the mass ratio of the material, the conductive agent and the binder is 8:1: 1.
The application of the novel water system zinc ion battery anode material is as follows: and uniformly mixing, wherein the mixing mode comprises one or more of manual grinding, mechanical ball milling and mechanical stirring, and the mixing time is 0.5-24 h.
The application of the novel water system zinc ion battery anode material is as follows: the novel water system zinc ion battery also comprises a negative electrode and electrolyte, wherein the negative electrode is metal zinc, and the electrolyte is 2mol/L ZnSO4+0.1mol/L MnSO4The mixed solution of (1).
The invention also aims to overcome the defects in the prior art and provide a novel water-based zinc ion battery anode material, and the novel water-based zinc ion battery prepared from the material has a voltage window of 0.8-1.8V and 300mA g-1Under the current density, the voltage platform with the voltage of 1.6-1.8V has the voltage of more than 175mA h g in the first 100 cycles-1The reversible specific capacity of (a).
The invention has the beneficial effects that:
(1) the invention provides a positive material ZnMnO of a novel zinc ion battery3The obtained ZnMnO3The material is applied to the positive electrode of a zinc ion battery, and zinc ions are generated on a zinc sheet of a negative electrode in the charge-discharge process of the zinc ion battery and are transferred to a positive electrode ZnMnO3Moving in the direction of the material, in ZnMnO3In and out of the ZnMnO3The positive electrode material is very suitable for the water-system zinc ion battery, and the prepared water-system zinc ion battery has excellent electrochemical performance.
(2) The invention relates to a new typeAqueous zinc ion battery, and commercially available monometallic manganese dioxide (MnO) which has been reported so far2) Manganese oxide (Mn)2O3) Compared with the zinc ion battery prepared by the method, the zinc ion battery has higher initial specific capacity, rate capability and cycling stability; it is at 300mA g-1After 150 cycles under the current density, the capacity retention rate is good; at 1000mA g-1After the circulation under the high current density, when the current density is recovered to 300mA g-1When the discharge capacity is kept at 175mA h g-1The level of (c).
(3) The novel water-based zinc ion battery prepared by the invention is compared with the existing single metal manganese-based oxides such as (MnO )2，Mn2O3，Mn3O4) Compared with the zinc ion battery, the prepared zinc ion battery has the advantages of low price of raw materials, simple required equipment and ZnMnO generation3The material has the advantages of less energy sources, shorter required time, high material purity and the like, and meets the green and environment-friendly requirements of high specific capacity and low cost of the zinc ion battery anode material.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 shows ZnMnO prepared in example 13XRD pattern of the material.
FIG. 2 shows ZnMnO prepared in example 13SEM image of material.
FIG. 3 shows ZnMnO prepared in example 13Elemental mapping of materials.
FIG. 4 shows ZnMnO obtained in example 13CV curve of zinc ion battery composed of the material.
FIG. 5 shows ZnMnO obtained in example 13Cycle profile of zinc ion battery composed of the material.
FIG. 6 shows ZnMnO obtained in example 13The multiplying power performance diagram of the zinc ion battery composed of the material.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The preparation of the zinc ion battery adopts the conventional means in the field, namely, the metal zinc is taken as a counter electrode, and 2mol/L ZnSO is taken4+0.1mol/L MnSO4The mixed solution of (A) is used as an electrolyte and ZnMnO is used3Assembling the button cell by using the anode material; the electrochemical performance of the prepared battery is tested by using a Shenzhen Xinwei BST-5V type battery tester, and the charge-discharge voltage range is 0.8V-1.8V (vs.Zn)2+Zn), the test temperature was 25 ℃.
Example 1
2.231g Zn (NO)3)2·6H2O，2.685g Mn(NO3)2And 1.198g of sucrose is dissolved in 5mL of deionized water, transferred to a 200mL beaker, magnetically stirred for 30min, then transferred to a forced air drying oven, and puffed for 3 hours at 140 ℃ to obtain a sintering precursor.
Calcining the precursor fluffy powder for 2 hours at 500 ℃ in the air atmosphere to obtain ZnMnO3A material.
Example 2
2.231g Zn (NO)3)2·6H2O，2.685g Mn(NO3)2And 1.198g of sucrose is dissolved in 5mL of deionized water, transferred to a 200mL beaker, magnetically stirred for 30min, then transferred to a forced air drying oven, and puffed at 140 ℃ for 3 hours to obtain a sintered precursor.
Calcining the precursor fluffy powder for 2 hours at 600 ℃ in the air atmosphere, cooling and grinding to obtain ZnMnO3A material.
Example 3
2.231g Zn (NO)3)2·6H2O，2.685g Mn(NO3)2And 1.198g of sucrose is dissolved in 5mL of deionized water, transferred to a 200mL beaker, magnetically stirred for 30min, then transferred to a forced air drying oven, and puffed at 140 ℃ for 3 hours to obtain a sintered precursor.
Calcining the precursor fluffy powder for 2 hours at 700 ℃ in air atmosphere, cooling and grinding to obtain ZnMnO3A material.
Example 4
2.231g Zn (NO)3)2·6H2O，2.685g Mn(NO3)2And 1.198g of sucrose is dissolved in 5mL of deionized water, transferred to a 200mL beaker, magnetically stirred for 30min, then transferred to a forced air drying oven, and puffed at 180 ℃ for 3 hours to obtain a sintered precursor.
Calcining the obtained precursor fluffy powder for 2 hours at 500 ℃ in the air atmosphere, cooling and grinding to obtain ZnMnO3A material.
Example 5
2.231g Zn (NO)3)2·6H2O，2.685g Mn(NO3)2And 1.198g of sucrose is dissolved in 5mL of deionized water, transferred to a 200mL beaker, magnetically stirred for 30min, then transferred to a forced air drying oven, and puffed at 180 ℃ for 3 hours to obtain a sintered precursor.
Calcining the precursor fluffy powder for 2 hours at 600 ℃ in the air atmosphere, cooling and grinding to obtain ZnMnO3A material.
Example 6
2.231g Zn (NO)3)2·6H2O，2.685g Mn(NO3)2And 1.198g of sucrose is dissolved in 5mL of deionized water, transferred to a 200mL beaker, magnetically stirred for 30min, then transferred to a forced air drying oven, and puffed at 180 ℃ for 3 hours to obtain a sintered precursor.
Calcining the precursor fluffy powder for 2 hours at 700 ℃ in air atmosphere, cooling and grinding to obtain ZnMnO3A material.
ZnMnO prepared in example 13The X-ray diffraction experiment was carried out, and the results are shown in FIG. 1. The diffraction pattern of the material and ZnMnO can be known from the figure3The standard card is completely matched, and the crystallinity of the material is higher. ZnMnO prepared by the method3Belonging to the F space group.
ZnMnO prepared in example 13Scanning electron microscopy was performed, and the results are shown in FIG. 2. The invention adopts a sol-gel method to prepare ZnMnO3The material is granular, and the particle size of the material is 20-50 nm.
ZnMnO prepared in example 13Elemental analysis was performed, and the results are shown in FIG. 3. ZnMnO can be confirmed from the element map3In the material, Zn, Mn and O elements are uniformly distributed.
ZnMnO prepared in examples 1 to 63The electrochemical performance of the material is tested, experiments show that the material is feasible in application of the anode material of the water-based zinc ion battery, and the electrochemical performance of the material obtained at the puffing temperature of 140 ℃ and the calcining temperature of 600 ℃ is more excellent.
Example 7
ZnMnO is added3The material is uniformly mixed with a conductive agent and a binder, coated on a titanium foil, and then dried in a drying oven at 80 ℃ for 12 hours to obtain the novel anode piece of the water system zinc ion battery. Using metal zinc as a counter electrode and 2mol/L ZnSO4+0.1mol/L MnSO4The mixed solution of (A) and (B) is used as an electrolyte, and the obtained ZnMnO is3The positive pole piece of the material is assembled into a button cell. Shenzhen Xinwei BST-5V type battery testerAnd carrying out electrochemical performance test on the alloy.
The resulting FIG. 4 is ZnMnO3Cyclic voltammogram of the material, we see ZnMnO3When the zinc ion battery positive electrode material is used as a zinc ion battery positive electrode material, an oxidation reduction peak can be well observed, which shows that ZnMnO is3Is very suitable for the anode material of the water-based zinc ion battery. Meanwhile, the peak current of the redox peak gradually increases from the first turn to the third turn of the scan, indicating that the electrode material is a process of gradual activation during the initial electrochemical reaction.
FIG. 5 shows the button cell prepared above at 300mA g-1The electrochemical performance chart under the current density still has good capacity retention rate even after 150 cycles, which shows that ZnMnO3The electrode has good stability and higher specific capacity.
FIG. 6 is a graph showing the rate performance of the button cell prepared in the above way under different current densities, and ZnMnO was prepared3Electrode materials at 100, 200, 300, 500 and 1000mA g-1ZnMnO in the charge and discharge test at the current density of (2)3The electrodes showed specific discharge capacities of 182.5, 173.3, 166.2, 156.9 and 134.5mAhg, respectively-1. Even at 1000mA g-1When the current density is recovered to 300mAg after the circulation under the high current density-1The specific discharge capacity is still kept at 175mAhg-1The level (b) indicates that the aqueous zinc-ion battery obtained by the present invention has excellent rate performance.
The invention provides a positive material ZnMnO of a novel zinc ion battery3The obtained ZnMnO3The material is applied to the positive electrode of a zinc ion battery, and zinc ions are generated on a zinc sheet of a negative electrode in the charge-discharge process of the zinc ion battery and are transferred to a positive electrode ZnMnO3Moving in the direction of the material, in ZnMnO3In and out of the ZnMnO3The positive electrode material is very suitable for the water-system zinc ion battery, and the prepared water-system zinc ion battery has excellent electrochemical performance.
The novel water-based zinc ion battery prepared by the invention is compared with the commercial monometallic manganese dioxide (MnO) reported at present2) And (2) a metal oxideManganese (Mn)2O3) Compared with the zinc ion battery prepared by the method, the zinc ion battery has higher initial specific capacity, rate capability and cycling stability; it is at 300mA g-1After 150 cycles under the current density, the capacity retention rate is good; at 1000mA g-1After the circulation under the high current density, when the current density is recovered to 300mA g-1When the discharge capacity is kept at 175mA h g-1The level of (c).
The novel water-based zinc ion battery prepared by the invention is compared with the existing single metal manganese-based oxides such as (MnO )2，Mn2O3，Mn3O4) Compared with the zinc ion battery, the prepared zinc ion battery has the advantages of low price of raw materials, simple required equipment and ZnMnO generation3The material has the advantages of less energy sources, shorter required time, high material purity and the like, and meets the green and environment-friendly requirements of high specific capacity and low cost of the zinc ion battery anode material.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A preparation method of a novel water system zinc ion battery anode material is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
adding zinc salt, manganese salt and sucrose into a solvent, uniformly mixing, and performing magnetic stirring under the condition of water bath to form sol;
transferring the obtained sol into a forced air drying box for puffing to obtain a sintering precursor;
sintering the fluffy precursor in the atmosphere;
cooling and grinding to obtain ZnMnO used as the anode material of the zinc ion battery3。
2. The method for producing a novel aqueous zinc-ion battery positive electrode material according to claim 1, characterized in that: the zinc salt comprises any one of zinc nitrate, zinc sulfate and zinc chloride; the manganese salt comprises any one of manganese nitrate and manganese sulfate; the solvent comprises deionized water.
3. The method for producing a novel aqueous zinc-ion battery positive electrode material according to claim 1 or 2, characterized in that: adding zinc salt, manganese salt and sucrose into a solvent, and uniformly mixing, wherein the molar ratio of the zinc salt to the manganese salt is 1:1, and the molar ratio of the mixed salt of the zinc salt and the manganese salt to the sucrose is 1: 3.
4. The method for producing a novel aqueous zinc-ion battery positive electrode material according to claim 1 or 2, characterized in that: the puffing is carried out for 3 hours at the temperature of 120-180 ℃; and sintering the fluffy precursor in the atmosphere, wherein the temperature rise rate of the sintering is 1-20 ℃/min, the sintering temperature is 500-700 ℃, and the sintering time is 1-5 h.
5. The method for producing a novel aqueous zinc-ion battery positive electrode material according to claim 4, characterized in that: the puffing temperature is 140 ℃, and the calcining temperature is 600 ℃.
6. The method for producing a novel aqueous zinc-ion battery positive electrode material according to claim 4, characterized in that: the atmosphere is air or oxygen.
7. The application of the product prepared by the preparation method of the novel water-based zinc ion battery positive electrode material in the preparation of the novel water-based zinc ion battery positive electrode is characterized in that: the use of said composition, comprising,
ZnMnO is added3Uniformly mixing the material with a conductive agent and a binder, coating the mixture on a titanium foil, and drying the titanium foil in a drying oven at the temperature of 80 ℃ for 12 hours to obtain the novel water-based zinc ion battery positive pole piece; wherein,
the conductive agent comprises acetylene black;
the binder comprises polyvinylidene fluoride;
ZnMnO3the mass ratio of the material, the conductive agent and the binder is 8:1: 1.
8. The use of claim 7, wherein: and uniformly mixing, wherein the mixing mode comprises one or more of manual grinding, mechanical ball milling and mechanical stirring, and the mixing time is 0.5-24 h.
9. The use of claim 7, wherein: the novel water system zinc ion battery also comprises a negative electrode and electrolyte, wherein the negative electrode is metal zinc, and the electrolyte is 2mol/L ZnSO4+0.1mol/L MnSO4The mixed solution of (1).
10. The use of claim 7, wherein: the novel water system zinc ion battery is used for charging the zinc ion battery at a voltage window of 0.8-1.8V and 300mA g-1Under the current density, the voltage platform with the voltage of 1.6-1.8V has the voltage of more than 175mA h g in the first 100 cycles-1The reversible specific capacity of (a).
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