CN116826026B - Organic/inorganic composite positive electrode material and preparation method and application thereof - Google Patents
Organic/inorganic composite positive electrode material and preparation method and application thereof Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000006258 conductive agent Substances 0.000 claims abstract description 40
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 50
- 239000006230 acetylene black Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 230000010287 polarization Effects 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 20
- 229940071125 manganese acetate Drugs 0.000 claims description 12
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 11
- 238000011065 in-situ storage Methods 0.000 claims description 10
- 238000004070 electrodeposition Methods 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 6
- 229940075397 calomel Drugs 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000002077 nanosphere Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 238000009830 intercalation Methods 0.000 abstract description 9
- 230000002687 intercalation Effects 0.000 abstract description 9
- 239000011701 zinc Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000004146 energy storage Methods 0.000 abstract description 4
- 239000011229 interlayer Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000005416 organic matter Substances 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 description 18
- 239000004744 fabric Substances 0.000 description 18
- 239000002002 slurry Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 238000002156 mixing Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- -1 polyparaphenylene Polymers 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- 239000010405 anode material Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 230000005660 hydrophilic surface Effects 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [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
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Abstract
The application relates to an organic/inorganic composite positive electrode material, a preparation method and application thereof, belonging to the technical field of electrochemical energy storage; the positive electrode material comprises a conductive agent and a manganese dioxide layer deposited on the conductive agent, wherein the manganese dioxide layer is intercalated with poly-p-phenol; the manganese dioxide layer is intercalated by the poly-p-phenol molecules which can be introduced with multiple active groups as MnO 2 Additional theoretical specific capacity is provided and intercalation of the polypara-phenol molecules adjusts the interlayer spacing to promote reaction kinetics facilitating ion diffusion between manganese dioxide plates. The poly-p-phenol has stability as an organic matter, and the molecular weight is increased after electrochemical polymerization, so that the conductivity and the structural integrity of the composite positive electrode are improved. The pre-intercalated poly-p-phenol containing multiple active sites (c=o) enables the organic/inorganic composite positive electrode material to be reacted with Zn 2+ /H + And the energy storage characteristic of the water system zinc ion battery is optimized under the co-embedding synergistic effect.
Description
Technical Field
The application relates to the technical field of electrochemical energy storage, in particular to an organic/inorganic composite positive electrode material, a preparation method and application thereof.
Background
Due to the urgent demands for environmental friendliness and outstanding safety, aqueous Zinc Ion Batteries (AZIBs) are expected to be one of the most promising safety batteries. The advantages of safety, reliability, environmental friendliness, low cost and simple process of the water-based zinc ion battery make the water-based zinc ion battery pay attention to the application market of large-scale energy storage, consumer electronics and flexible wearable electronics. The water-based zinc ion battery mainly comprises an anode and a cathode and electrolyte. In recent years, the positive electrode material of the water-based zinc battery is continuously developed and mainly comprises manganese dioxide with different crystal forms, prussian blue and analogues, vanadium-based oxide and an organic electrode. Manganese dioxide is used in many cases because of its excellent theoretical specific capacity and advantages of manganese element in various valence states. However, because of the poor intrinsic conductivity and the easy collapse of the structure, the electronic state and the structural stability of the manganese dioxide bulk phase are required to be regulated and controlled during the use, and the method can be mainly divided into defect engineering, intercalation engineering and interface engineering. However, the electrical performance of the current regulated positive electrode material still needs to be improved, in particular to a water-based zinc-manganese battery system based on pre-intercalation modified manganese dioxide.
Disclosure of Invention
The application provides an organic/inorganic composite positive electrode material, a preparation method and application thereof, so as to improve the electrical property of the positive electrode material.
In a first aspect, the present application provides an organic/inorganic composite positive electrode material comprising a conductive agent and a manganese dioxide layer deposited on the conductive agent, the manganese dioxide layer having a poly-p-phenol intercalated therein.
As an alternative embodiment, in the positive electrode material, in the manganese dioxide layer, the mass ratio of manganese dioxide to poly-p-phenol is (0.5 to 1.5): (0.5 to 1.5).
As an optional implementation mode, in the positive electrode material, the loading amount of the manganese dioxide layer on the conductive agent is 1.0-7.0 mg/cm 2 。
As an alternative embodiment, the conductive agent includes acetylene black.
In a second aspect, the present application provides a method for preparing an organic/inorganic composite positive electrode material, the method comprising:
obtaining a conductive agent substrate layer;
and (3) depositing manganese dioxide and poly-p-phenol on the conductive agent of the conductive agent substrate layer in situ, and carrying out polarization treatment to obtain the anode material.
As an alternative embodiment, the depositing manganese dioxide and polypara-phenol in situ on the conductive agent substrate layer, and then performing polarization treatment to obtain the positive electrode material includes:
and taking the conductive agent substrate layer as a working electrode, putting the working electrode into a three-electrode system of sulfuric acid, manganese acetate and p-phenol, taking a platinum sheet and a calomel electrode as a counter electrode and a reference electrode respectively, carrying out electrochemical deposition to polymerize manganese dioxide and p-phenol and deposit the manganese dioxide and the p-phenol on the conductive agent of the conductive agent substrate layer in situ, and carrying out polarization treatment to obtain the anode material.
As an alternative embodiment, the current density of the electrochemical deposition is 5-20 mA/cm 2 ；
The time of the electrochemical deposition is 20-300 s;
the molar concentration of the sulfuric acid is 0.005-0.015 mol/L;
the molar concentration of the manganese acetate is 0.05-0.15 mol/L;
the molar concentration of the p-phenol is 0.03-0.1 mol/L.
As an optional implementation manner, the potential of the polarization treatment is 1-1.2 v;
the time of the polarization treatment is 50-300 s.
In a third aspect, the present application provides a positive electrode sheet, the positive electrode sheet including a current collector and a positive electrode material layer attached to the current collector, the positive electrode material layer including the positive electrode material according to the first aspect or the positive electrode material produced by the production method according to the second aspect.
In a fourth aspect, the application provides a zinc ion battery, which comprises the positive plate of the third aspect, 2 mol/L zinc sulfate electrolyte and a high-purity metal zinc negative electrode with a thickness of 100 microns, and the battery is assembled into a CR2032 battery in a sealing manner under the pressure of 50-70 MPa for electrochemical performance testing.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
according to the anode material provided by the embodiment of the application, the manganese dioxide layer is intercalated by the poly-p-phenol molecules, the poly-p-phenol molecules can be introduced into multiple active groups to provide additional theoretical specific capacity for manganese dioxide, and the intercalation of the poly-p-phenol molecules adjusts the interlayer spacing to promote reaction kinetics, so that ions are facilitated to diffuse between the layers. Meanwhile, the poly-p-phenol has stability as an organic matter, and the molecular weight is increased after electrochemical polymerization, so that the structural stability is further improved. Thus, the multiple active sites (c=o and mn—o) within the intercalated organics can react with Zn of manganese dioxide 2+ /H + The co-embedding mechanism cooperates to optimize the energy storage characteristic of the obtained water system zinc ion battery.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a flow chart of a method provided by an embodiment of the present application;
FIG. 2 is an elemental distribution diagram of a positive electrode material provided in example 1 of the present application;
fig. 3 is a scanning electron microscope image of the positive electrode material provided in embodiment 1 of the present application, a in fig. 3 and b in fig. 3 are scanning electron microscope images of the positive electrode material provided in embodiment 1, and c in fig. 3 and d in fig. 3 are scanning electron microscope images of the positive electrode material provided in comparative example 1;
fig. 4 is a schematic structural diagram of the positive electrode material provided in embodiment 1 of the present application;
FIG. 5 is a charge-discharge long cycle chart at a current density of 100 mA/g for the positive electrode material provided in example 1 of the present application as a positive electrode for a zinc-ion battery;
FIG. 6 is a long cycle chart of charge and discharge at a current density of 500 mA/g for the positive electrode material provided in example 1 of the present application as a positive electrode for a zinc-ion battery;
FIG. 7 is a graph showing the charge and discharge curves of the positive electrode material provided in example 1 of the present application as the positive electrode of a zinc ion battery, wherein the constant current charge and discharge uses current densities of 0.1, 0.2, 0.5, 1, 2, 3, 5, 8, 10A/g, respectively;
fig. 8 is a charge-discharge long cycle comparison chart of the positive electrode materials provided in example 1, comparative example 1 and comparative example 2 of the present application as the positive electrode of the zinc ion battery at a current density of 500 mA/g, respectively.
Fig. 9 is a charge-discharge long cycle comparison chart of the positive electrode materials provided in example 1, comparative example 1 and comparative example 2 of the present application as the positive electrode of the zinc ion battery at a current density of 1000mA/g, respectively.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
Unless specifically indicated otherwise, the various raw materials, reagents, instruments, equipment, and the like used in this application are commercially available or may be prepared by existing methods.
The embodiment of the application provides an organic/inorganic composite positive electrode material, which comprises a conductive agent and a manganese dioxide layer deposited on the conductive agent, wherein polyparaphenylene oxide is intercalated in the manganese dioxide layer. The positive electrode material was designated as CMO-PQ.
In some embodiments, in the positive electrode material, in the manganese dioxide layer, a mass ratio of manganese dioxide to poly-p-phenol is (0.5 to 1.5): (0.5 to 1.5); in the positive electrode material, the loading capacity of the manganese dioxide layer on the conductive agent is 1.0-7.0 mg/cm 2 . The conductive agent includes acetylene black.
According to the anode material, the manganese dioxide layer is intercalated by the poly-p-phenol molecules, the poly-p-phenol molecules can be introduced into multiple active groups to provide additional theoretical specific capacity for manganese dioxide, and the intercalation of the poly-p-phenol molecules adjusts the interlayer spacing to promote reaction kinetics, so that the diffusion of ions between laminates is facilitated. Meanwhile, the poly-p-phenol has stability as an organic matter, and the molecular weight is increased after electrochemical polymerization, so that the structural stability is further improved. Thus, as shown in fig. 4, the multiple active sites (c=o and mn—o) of the pre-intercalated organic matter can be reacted with Zn 2+ /H + And the energy storage characteristics of the Zn// CMO-PQ battery are optimized under the co-embedded synergistic effect.
The positive electrode material has excellent electrochemical performance in a water-based zinc ion battery, and can obtain a higher specific capacity of 410 mAh/g under a small current density of 100 mA/g; at a high current density of 10A/g, the specific capacity was 90 mAh/g, and good rate capability was exhibited. Compared with a manganese dioxide positive electrode material (CMO) without the intercalation of the poly-p-phenol, the stability of the material is obviously better than that of a comparison sample, and the poly-p-Phenol (PQ) serving as a flexible intercalation molecule can be proved to not only improve the specific capacity and the rate capability, but also stabilize the structural integrity of the CMO-PQ electrode material.
Fig. 1 is a flowchart of a method provided in an embodiment of the present application, and as shown in fig. 1, based on a general inventive concept, the embodiment of the present application further provides a method for preparing an organic/inorganic composite cathode material, where the method includes:
s1, obtaining a conductive agent substrate layer;
specifically, in the present embodiment, the area is 2×2 cm 2 The Carbon Cloth (CC) of (C) is treated with concentrated nitric acid to form a hydrophilic surface. By mixing acetylene black (ACET) and polyvinylidene fluoride in a mass ratio of 9:1 into N-methylpyrrolidone to prepare an ACET slurry. And coating ACET slurry on the carbon cloth, and drying at 80 ℃ for 6 hours to obtain the conductive agent substrate layer.
S2, depositing manganese dioxide and poly-p-phenol on the conductive agent of the conductive agent substrate layer in situ, and carrying out polarization treatment to obtain the anode material.
In some embodiments, the in situ deposition of manganese dioxide and poly-p-phenol onto the conductive agent substrate layer followed by a polarization treatment to obtain a positive electrode material comprises:
and taking the conductive agent substrate layer as a working electrode, putting the working electrode into a three-electrode system of sulfuric acid, manganese acetate and p-phenol, taking a platinum sheet and a calomel electrode as a counter electrode and a reference electrode respectively, carrying out electrochemical deposition to polymerize manganese dioxide and p-phenol and deposit the manganese dioxide and the p-phenol on the conductive agent of the conductive agent substrate layer in situ, and carrying out polarization treatment to obtain the anode material.
Further, the current density of the electrochemical deposition is 5-20 mA/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The time of the electrochemical deposition is 20-300 s; the molar concentration of the sulfuric acid is 0.005-0.015 mol/L; the molar concentration of the manganese acetate is 0.05-0.15 mol/L; the molar concentration of the p-phenol is 0.03-0.1 mol/L. The potential of the polarization treatment is 1-1.2V; the time of the polarization treatment is 50-300 s.
Specifically, in this example, a carbon cloth coated with a conductive carbon black (ACET) slurry was placed in a slurry containing 0.01 mol/L sulfuric acidAnd 0.1mol/L manganese acetate and p-phenol (0.03 mol/L, 0.06 mol/L and 0.1 mol/L) electrolyte with different concentrations are carried out for 20-300 seconds in a three-electrode system with a certain current density, wherein a counter electrode adopts a Pt sheet, and a reference electrode adopts Ag/AgCl (saturated potassium chloride); then using potentiostatic polarization mode at 1.1V for 50-300 s, the polarization time and the ACET quality (less than 1 mg/cm) 2 ) To control the active load quality of CMO-PQ, and the range is controlled to be 1.0-7.0 mg/cm 2 . Finally, the obtained CMO-PQ electrode was thoroughly washed with distilled water, and then dried at 80℃for 24 hours to obtain a positive electrode material.
Based on one general inventive concept, the present embodiments also provide a positive electrode sheet including a positive electrode material layer including the positive electrode material provided as above or the positive electrode material manufactured by the manufacturing method provided as above.
The positive electrode plate is realized based on the positive electrode material, and the specific content of the positive electrode material can refer to the above embodiment, and because the positive electrode plate adopts part or all of the technical schemes of the above embodiment, at least has all the beneficial effects brought by the technical schemes of the above embodiment, and the details are not repeated here.
Based on one general inventive concept, embodiments of the present application also provide a zinc ion battery including the positive electrode sheet provided above.
Specifically, in this embodiment, the zinc ion battery specifically includes: the CMO-PQ composite material pole piece prepared in situ is an anode electrode pole piece, zinc metal is a cathode pole piece, and electrolyte is zinc sulfate solution with the concentration of 2 mol/L.
The present application is further illustrated below in conjunction with specific examples. It should be understood that these examples are illustrative only of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Example 1
A method of preparing a positive electrode material, the method comprising:
s1, the area is 2 multiplied by 2 cm 2 The Carbon Cloth (CC) of (C) is treated with concentrated nitric acid to form a hydrophilic surface. By mixing acetylene black (ACET) and polyvinylidene fluoride in a mass ratio of 9:1 into N-methylpyrrolidone to prepare an ACET slurry. Then coating ACET slurry on carbon cloth, and drying at 80 ℃ for 6 hours to obtain a conductive agent substrate layer;
s2, placing carbon cloth coated with ACET slurry in a three-electrode system of 100 mL deionized water, mixing 0.01 mol/L sulfuric acid, 0.1mol/L manganese acetate and 0.03 mol/L electrolyte of p-phenol, and carrying out 150 seconds at a certain current density, wherein a counter electrode adopts a Pt sheet, and a reference electrode adopts Ag/AgCl (saturated potassium chloride); potentiostatic polarization mode 175s was then used at 1.1V. Finally, the obtained CMO-PQ electrode was thoroughly washed with distilled water, and then dried at 80℃for 24 hours to obtain a positive electrode material.
Example 2
A method of preparing a positive electrode material, the method comprising:
s1, the area is 2 multiplied by 2 cm 2 The Carbon Cloth (CC) of (C) is treated with concentrated nitric acid to form a hydrophilic surface. By mixing acetylene black (ACET) and polyvinylidene fluoride in a mass ratio of 9:1 into N-methylpyrrolidone to prepare an ACET slurry. Then coating ACET slurry on carbon cloth, and drying at 80 ℃ for 6 hours to obtain a conductive agent substrate layer;
s2, placing carbon cloth coated with ACET slurry in a three-electrode system of 100 mL deionized water, mixing 0.01 mol/L sulfuric acid, 0.1mol/L manganese acetate and 0.06 mol/L electrolyte of p-phenol, and carrying out 150s at a certain current density, wherein a counter electrode adopts a Pt sheet, and a reference electrode adopts Ag/AgCl (saturated potassium chloride); the potentiostatic polarization mode was then used at 1.1V for 175 seconds. Finally, the obtained CMO-PQ electrode was thoroughly washed with distilled water, and then dried at 80℃for 24 hours to obtain a positive electrode material.
Example 3
A method of preparing a positive electrode material, the method comprising:
s1, setting the area as 2×2 cm 2 The Carbon Cloth (CC) of (C) is treated with concentrated nitric acid to form a hydrophilic surface. By mixing acetylene black (ACET) and polyvinylidene fluoride in a mass ratio of 9:1 into N-methylpyrrolidone to prepare an ACET slurry. Then coating ACET slurry on carbon cloth, and drying at 80 ℃ for 6 hours to obtain a conductive agent substrate layer;
s2, placing carbon cloth coated with ACET slurry in a three-electrode system of 100 mL deionized water, mixing 0.01 mol/L sulfuric acid, 0.1mol/L manganese acetate and 0.1mol/L electrolyte of p-phenol, and carrying out 150s at a certain current density, wherein a counter electrode adopts a Pt sheet, and a reference electrode adopts Ag/AgCl (saturated potassium chloride); potentiostatic polarization mode 175s was then used at 1.1V. Finally, the obtained CMO-PQ electrode was thoroughly washed with distilled water, and then dried at 80℃for 24 hours to obtain a positive electrode material.
Comparative example 1
A method of preparing a positive electrode material, the method comprising:
s1, the area is 2 multiplied by 2 cm 2 Carbon Cloth (CC) of (2) is treated by concentrated nitric acid to form a hydrophilic surface;
s2, placing the treated carbon cloth in a three-electrode system of 100 mL deionized water, mixing 0.01 mol/L sulfuric acid, 0.1mol/L manganese acetate and 0.03 mol/L electrolyte of p-phenol, and carrying out 150s at a certain current density, wherein a counter electrode adopts a Pt sheet, and a reference electrode adopts Ag/AgCl (saturated potassium chloride); potentiostatic polarization mode 175s was then used at 1.1V. Finally, the obtained CMO-PQ electrode was thoroughly washed with distilled water, and then dried at 80℃for 24 hours to obtain a positive electrode material (i.e., mnO) 2 /PHQ）。
Comparative example 2
A method of preparing a positive electrode material, the method comprising:
s1, the area is 2 multiplied by 2 cm 2 The Carbon Cloth (CC) of (C) is treated with concentrated nitric acid to form a hydrophilic surface. By mixing acetylene black (ACET) and polyvinylidene fluoride in a mass ratio of 9:1 into N-methylpyrrolidone to prepare an ACET slurry. Then coating ACET slurry on carbon cloth, and drying at 80 ℃ for 6 hours to obtain a conductive agent substrate layer;
s2, placing carbon cloth coated with ACET slurry in a three-electrode system of 100 mL deionized water and mixing 0.01 mol/L sulfuric acid and 0.1mol/L manganese acetate electrolyte, and carrying out 150s at a certain current density, wherein a counter electrode adopts a Pt sheet, and a reference electrode adopts Ag/AgCl (saturated potassium chloride); potentiostatic polarization mode 175s was then used at 1.1V. Finally, the obtained CMO-PQ electrode was thoroughly washed with distilled water, and then dried at 80℃for 24 hours to obtain a positive electrode material (i.e., ACET@MnO 2 ）。
The element distribution test was performed on the cathode materials provided in examples 1 to 3, and the results are illustrated by the test results of example 1 only, and the results are shown in fig. 2, and fig. 2 is a graph showing the element distribution of the cathode materials provided in example 1, wherein nano spherical manganese dioxide is uniformly distributed on carbon cloth fibers, so as to successfully prove the synthesis of CMO-PQ electrode materials.
The positive electrode materials provided in examples 1 to 3 and comparative example 1 were subjected to the sem test, and since the results have similarities, the test results of example 1 are merely exemplified below, and the results are shown in fig. 3, a in fig. 3 and b in fig. 3 are the sem images of the positive electrode materials provided in example 1, and c in fig. 3 and d in fig. 3 are the sem images of the positive electrode materials provided in comparative example 1. According to the graph, the specific surface area of the electrodeposited manganese dioxide nanowire sphere can be increased by adding ACET, the wettability of the obtained CMO-PQ electrode and electrolyte and the conductivity of the CMO-PQ electrode are improved, and a water-based zinc ion battery with quick reaction kinetics is constructed.
The positive electrode materials provided in examples 1 to 3 were subjected to long cycle test of charge and discharge, and the results are illustrated by the test results of example 1 only, and the results are shown in fig. 5 and 6, wherein fig. 5 and 6 are respectively long cycle charts of charge and discharge of the positive electrode materials provided in example 1 as positive electrodes of zinc ion batteries at current densities of 100 mA/g and 500 mA/g, and the charts show that the pre-intercalation strategy of the organic matters provides the CMO-PQ positive electrode material with excellent structural stability and cycle life. The capacity retention close to its theoretical specific capacity (308 mAh/g) can be maintained even at a small current density. The meaning represented by the left arrow in fig. 5 is: the corresponding curve is the specific capacity at different turns, and the right arrow represents the meaning: corresponding to coulombic efficiency at different turns. 0.1A/g in FIG. 5: the positive electrode material was used as the positive electrode of a zinc ion battery with a current density of 100 milliamperes per gram. 0.5A/g in FIG. 6: the positive electrode material was used as a positive electrode of a zinc ion battery at a current density of 500 milliamperes per gram.
The positive electrode materials provided in examples 1 to 3 were subjected to charge and discharge tests, and the results are similar, and the test results of example 1 are merely illustrated below, and the results are shown in fig. 7, and fig. 7 is a graph showing that the positive electrode material provided in example 1 is used as a charge and discharge curve of a positive electrode of a zinc ion battery, and current densities adopted by constant current charge and discharge are respectively 0.1, 0.2, 0.5, 1, 2, 3, 5, 8 and 10A/g, and as a result, PQ flexible molecules containing an electronegative (c=o) group can be used as "interlayer struts" to improve the ion diffusion rate of zinc ions between manganese dioxide layers, so that the CMO-PQ positive electrode still has good capacity retention rate at 10A/g.
The results of the charge-discharge long cycle test on the positive electrode materials provided in example 1, comparative example 1 and comparative example 2 are shown in fig. 8 and 9, and fig. 8 and 9 are respectively charge-discharge long cycle comparison diagrams of the positive electrode materials provided in example 1, comparative example 1 and comparative example 2 as the positive electrode of the zinc ion battery under the current density of 500 mA/g and 1000mA/g, as can be obtained from the diagrams, the synergy of ACET and organic intercalation enables the CMO-PQ positive electrode to have optimal specific capacity and cycle stability, and provides a new idea for the construction of advanced water-based zinc-manganese batteries.
In fig. 8, the meaning represented by the left arrow is: the corresponding curves represent the specific capacities of the CMO, CMO-PQ and CMO-PQ anodes at different turns, and the right arrow represents the meaning: the corresponding curves represent the coulombic efficiency of CMO, CMO-PQ and CMO-PQ anodes at different turns. The current density of the positive electrode material at 500 milliamp per gram as the positive electrode of the zinc ion battery is shown as 0.5A/g in fig. 8.
In fig. 9, the meaning represented by the left arrow is: the corresponding curves represent the specific capacities of the CMO and CMO-PQ anodes at different turns, the right arrow representing the meaning: the corresponding curves represent the coulombic efficiency of the CMO and CMO-PQ anodes at different turns. 1.0A/g in FIG. 9 represents the current density at 1000 milliamp per gram of the positive electrode material as the positive electrode of a zinc ion battery, respectively.
Various embodiments of the present application may exist in a range format; it should be understood that the description in a range format is merely for convenience and brevity and should not be interpreted as a rigid limitation on the scope of the application. It is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In this application, unless otherwise indicated, terms of orientation such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present application, the terms "include", "comprise", "comprising" and the like mean "including but not limited to". Relational terms such as "first" and "second", and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describing an association relationship of an association object means that there may be three relationships, for example, a and/or B, may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
The foregoing is merely a specific embodiment of the application to enable one skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (3)
1. A method for preparing an organic/inorganic composite positive electrode material comprising a conductive agent and a manganese dioxide layer deposited on the conductive agent, comprising:
obtaining a conductive agent substrate layer;
depositing manganese dioxide and poly-p-phenol on the conductive agent of the conductive agent substrate layer in situ, and carrying out polarization treatment to obtain a positive electrode material;
depositing manganese dioxide and poly-p-phenol on the conductive agent substrate layer in situ, and carrying out polarization treatment to obtain a positive electrode material, wherein the method comprises the following steps:
placing the conductive agent substrate layer serving as a working electrode into a three-electrode system containing sulfuric acid, manganese acetate and p-phenol electrolyte, respectively using a platinum sheet and a calomel electrode as a counter electrode and a reference electrode, performing electrochemical deposition to polymerize manganese dioxide and p-phenol and deposit the manganese dioxide and the p-phenol on the conductive agent of the conductive agent substrate layer in situ, and performing polarization treatment to obtain a positive electrode material;
the current density of the electrochemical deposition is 5-20 mA/cm 2 ；
The time of the electrochemical deposition is 20-300 s;
the molar concentration of the sulfuric acid is 0.005-0.015 mol/L;
the molar concentration of the manganese acetate is 0.05-0.15 mol/L;
the molar concentration of the p-phenol is 0.03-0.1 mol/L;
the potential of the polarization treatment is 1-1.2V;
the time of the polarization treatment is 50-300 s;
wherein, poly (p-phenol) is intercalated in the manganese dioxide layer; the manganese dioxide is in a nano sphere shape;
in the positive electrode material, in the manganese dioxide layer, the mass ratio of manganese dioxide to poly (p-phenol) is (0.5-1.5): (0.5 to 1.5); in the positive electrode material, the loading capacity of the manganese dioxide layer on the conductive agent is 1.0-7.0 mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The conductive agent includes acetylene black.
2. The positive electrode plate is characterized by comprising a current collector and a positive electrode material layer attached to the current collector, wherein the positive electrode material layer comprises an organic/inorganic composite positive electrode material prepared by the preparation method of the organic/inorganic composite positive electrode material in claim 1.
3. A zinc-ion battery comprising the positive electrode sheet of claim 2.
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