CN110655112B - Manganese oxide positive electrode material of water-based battery and preparation method and application thereof - Google Patents
Manganese oxide positive electrode material of water-based battery and preparation method and application thereof Download PDFInfo
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Abstract
The application discloses a manganese oxide positive electrode material of a water-based battery, and a preparation method and application thereof. The manganese oxide cathode material has a molecular formula of MnO 2 H x (H 2 O) y X is more than 0 and less than 1, and y is more than 0 and less than 1; during charging and discharging, the manganese oxide is embedded with H + And metal ions, H + In the form of Mn-OH, metal ions in the form of Mn-O-metal ions, and H + And metal ions are synergistically extracted or inserted in the manganese oxide cathode material. The cathode material of the application is characterized in that H is embedded in manganese oxide in situ in the form of Mn-OH + And the manganese oxide structure can be stabilized. During charging and discharging, H + The positive electrode material is embedded or separated from metal ions in a synergistic manner, so that the positive electrode material has higher capacity and better stability; at high magnification H + The insertion or extraction of (2) can promote the capacity exertion and make the positive electrode material have excellent rate performance.
Description
Technical Field
The application relates to the field of anode materials of water-based batteries, in particular to a manganese oxide anode material of a water-based battery, and a preparation method and application thereof.
Background
Water system electricityThe batteries include aqueous primary batteries and aqueous secondary batteries, and are classified into zinc ion batteries, lithium ion batteries, sodium ion batteries, potassium ion batteries, magnesium ion batteries, aluminum ion batteries, and the like according to metal ions. Renewable energy sources in China are very rich and comprise wind energy, solar energy, geothermal energy and the like, and electric energy generated by the new energy sources needs to be stored, so that large-scale energy storage devices have very wide development space in China. Slightly acidic Zn-MnO in water system 2 The secondary battery, namely the water system zinc ion battery prepared by adopting the manganese oxide anode material, has the advantages of low cost, high energy density, safety, stability, environmental friendliness and the like, and is very suitable for large-scale energy storage. In addition, the water system zinc ion battery has high application potential in the fields of automobile starting power supplies, low-cost electric vehicle power supplies and household energy storage. At present, Zn-MnO which is slightly acidic in water system 2 Secondary batteries are one of the most likely alternatives to lead acid batteries.
For 2010, Zn-MnO slightly acidic in water system was aimed at 2 Materials related to secondary batteries have been extensively studied. Zn-MnO 2 Mainly comprises manganese oxide anode material, zinc cathode and electrolyte. Among them, the manganese oxide positive electrode material is a key for determining the overall electrochemical performance of the aqueous secondary battery, and is also a key direction in the research field of aqueous zinc ion batteries. The manganese oxide positive electrode material is used not only in aqueous zinc ion batteries but also in other aqueous secondary batteries, such as lithium ion batteries, sodium ion batteries, potassium ion batteries, magnesium ion batteries, and aluminum ion batteries.
Compared with other water-based secondary battery anode materials such as prussian blue, vanadate and organic anode materials, the energy density of the manganese oxide anode material is as high as 308mAh g -1 The plateau voltage is as high as 1.4V vs. Zn/Zn 2+ The anode material has the advantages of high energy density, higher platform voltage, low cost, environmental friendliness, safety, stability and the like, and is the anode material of the most industrialized potential of the water-based secondary battery at present.
Oxides of manganese having a variety of crystal structures, including layered structures, e.g. delta-MnO 2 (ii) a Cellular structures, e.g. alpha-MnO 2 、β-MnO 2 、γ-MnO 2 And lambda-MnO 2 (ii) a Spinel structure, e.g. Mn 3 O 4 (ii) a And amorphous structures, e.g. electrodeposited MnO 2 . The crystal structures have different formation conditions, and H is generated in the charge and discharge processes + And Zn 2+ The intercalation/deintercalation mechanism has great difference, which causes the very obvious difference of the electrochemical properties of manganese oxides with different crystal structures.
In addition, during discharge, Mn 2+ The dissolution of (b) causes a rapid decay of the full cell performance, which is also one of the major problems to be solved for zinc ion batteries. Meanwhile, the intrinsic electronic conductivity of the manganese oxide is low, so that H in the charge and discharge processes of the manganese oxide is ensured + The resistance of metal ion insertion/separation is large, how to construct a good electronic conductive network for the manganese oxide anode material is also a water system Zn-MnO 2 One of the important problems to be solved in batteries and other aqueous secondary batteries.
Aiming at the characteristics of low intrinsic electronic conductivity, variable crystal structure and different charge-discharge mechanisms of manganese oxide, MnO is improved mainly by the following method 2 Electrochemical properties of the material: 1) the manganese oxide with nano scale, such as nanosheet layer, nanorod, nanofiber and the like, obtained through hydrothermal reaction is nano-sized, and the high specific surface area and small volume change of the nano material can well shorten H + And Zn 2+ Or the diffusion distance of other metal ions, the electrode reaction rate is improved, and the electrode cycle performance is improved; however, the nano material is easy to agglomerate, and the problems of high capacity and cycling stability cannot be fundamentally solved. 2) Regulating and controlling electrolyte by adding Mn into the electrolyte 2+ The dissolution of Mn in the discharge process of the manganese oxide is inhibited, and the stability of the anode material can be obviously improved; however, since the low cycle stability of manganese oxide is closely related not only to the elution of manganese but also to the collapse of the manganese oxide structure and the formation of an electrochemically inert phase during charge and discharge, Mn is present 2+ The addition of (2) does not essentially solve the problem of the cycle stability. 3) The conductive layer is coated by adopting a carbon-based material, such as graphene coating, carbon tube winding and the like, so that manganese can be remarkably reducedPolarization of oxide materials, increased capacity and cycling stability; however, this method involves a very complicated technical problem of dispersion of the carbon-based material and complexing with the manganese oxide, which leads to an increase in the production cost of the electrode and is not favorable for the advancement of industrialization. 4) The crystal structure is regulated, and the electrochemical performance and the structural stability of the manganese oxides with different crystal structures are greatly different; however, at present, few researches on the regulation and control of the crystal structure of the manganese oxide are carried out, and the existing manganese oxide is difficult to meet the increasingly developed use requirements in the aspects of capacity, cycle stability and rate performance.
Disclosure of Invention
The purpose of the present application is to provide an improved manganese oxide positive electrode material for aqueous batteries, and a preparation method and application thereof.
The following technical scheme is adopted in the application:
one aspect of the present application discloses a manganese oxide positive electrode material for an aqueous battery, the manganese oxide positive electrode material having a molecular formula of MnO 2 H x (H 2 O) y Wherein x is more than 0 and less than 1, and y is more than 0 and less than 1; during charging and discharging, the manganese oxide is embedded with H + And metal ions, H + In the form of Mn-OH, metal ions in the form of Mn-O-metal ions, H + And metal ions are synergistically extracted or inserted in the manganese oxide cathode material.
The key point of the manganese oxide cathode material is the special crystal structure, so that the manganese oxide cathode material can be embedded with H in the charge and discharge process + And metal ions of which H + Exists in the form of Mn-OH and can stabilize MnO 2 H x (H 2 O) y The function of the material structure. During charging and discharging, H + And metal ions in MnO 2 H x (H 2 O) y The materials are cooperatively removed or embedded, so that the manganese oxide anode material has higher capacity; at H + In the cyclic process of embedding or removing metal ions, the manganese oxide positive electrode material keeps good stability and has excellent electrochemical stability; h at high multiplying power + Is embedded orThe removal plays a great role in capacity exertion, so that the manganese oxide cathode material has excellent rate performance.
Preferably, the manganese oxide positive electrode material of the present application, and H + The metal ion which is synergistically inserted or extracted is Li + 、Na + 、K + 、Zn 2+ 、Mg 2+ And Al 3+ At least one of (1).
Preferably, the metal ion contains at least Zn 2+ 。
It is noted that the choice of metal ion is dependent on the particular cell type, e.g., in a zinc ion cell, then H is preferred + Is removed or inserted with zinc ions; however, in the zinc ion battery, in order to improve the battery performance, other metal elements may be doped in addition to zinc ions, and therefore, H may be present + And other metal ions are removed or inserted cooperatively. Other, lithium ion batteries, sodium ion batteries, potassium ion batteries, magnesium ion batteries, and the like, are similar and will not be described herein.
Preferably, the manganese oxide cathode material is a nanoparticle, nanowire or nanosheet.
Preferably, the thickness of the nanosheet is 1-10 nm, and the diameter of the nanosheet is 200-800 nm.
The application also discloses an application of the manganese oxide cathode material in an aqueous battery, wherein the aqueous battery is a primary battery or a secondary battery, and specifically, the aqueous battery is a zinc ion battery, a lithium ion battery, a sodium ion battery, a potassium ion battery, a magnesium ion battery or an aluminum ion battery.
It should be noted that the key of the present application lies in the improvement of the crystal structure of the manganese oxide positive electrode material itself, and as for the specific use in the preparation of primary batteries or secondary batteries, the requirements can be determined, and other components of the battery can also refer to the existing primary batteries or secondary batteries. In addition, as for the specific type of ion battery, it may be determined according to the requirements, including but not limited to zinc ion battery, lithium ion battery, sodium ion battery, potassium ion battery, magnesium ion battery, and aluminum ion battery.
The present application also discloses an aqueous primary battery or an aqueous secondary battery using the manganese oxide positive electrode material of the present application.
It can be understood that the aqueous primary battery or aqueous secondary battery of the present invention has higher capacity, better cycle stability and more excellent rate capability due to the use of the manganese oxide positive electrode material of the present invention, and thus can better satisfy different use requirements.
The application further discloses an application of the water-based primary battery or the water-based secondary battery in energy storage, 3C electronic products or new energy electric vehicles.
It is understood that the water-based primary battery or the water-based secondary battery according to the present invention has a higher capacity, better cycle stability, and more excellent rate capability, and thus can be preferably applied to various fields, such as energy storage, 3C electronic products, or new energy electric vehicles.
Preferably, the 3C electronic product of the present application mainly includes a mobile phone, a notebook computer and a tablet computer.
The application also discloses a preparation method of the manganese oxide anode material, which comprises the steps of adopting a high-temperature hydrothermal method, taking potassium permanganate and a carbon-based material as reactants, and synthesizing the manganese oxide anode material in one step; the reaction condition of the high-temperature hydrothermal method is 80-240 ℃ for 6-72 h.
The hydrothermal temperature influences the size and the crystallinity of the finally prepared manganese oxide nanometer petal structure, and the higher the temperature is, the larger the size of the nanometer petal is, and the better the crystallinity is. When the hydrothermal temperature is lower than 80 ℃, the carbon-based material and potassium permanganate do not react sufficiently; when the hydrothermal temperature is higher than 240 ℃, the prepared manganese oxide has overlarge grain size and poorer electrochemical performance. It can be understood that the nano petal structure prepared by the method is in a structural form enclosed by nano sheets, and the larger the size of the nano petals is, the larger the size of the corresponding nano sheet is, and the thickness and the diameter of the nano sheet are correspondingly increased. Therefore, the hydrothermal temperature can be adjusted according to factors such as the thickness and diameter of the nanosheet, and the degree of crystallinity required.
In the preparation method, the carbon-based material is used as a reducing agent to reduce potassium permanganate into manganese oxide; the carbon-based material is used as a reducing agent, and meanwhile, part of unreacted carbon material can promote the formation of a uniform and efficient conductive network, so that the electron transmission is facilitated, the electrode polarization is reduced, and the electrode rate performance is improved. The preparation method can be used for preparing the manganese oxide cathode material; moreover, the prepared manganese oxide anode material has fine particles, uniform distribution and excellent electrochemical performance; the preparation method has the advantages of simple process, mild conditions and low cost, and is particularly suitable for industrial large-scale production.
Preferably, the carbon-based material is at least one of charcoal, carbon black, carbon cloth, carbon paper, carbon fiber, acetylene black, SP, KS6, graphite, graphene oxide, redox graphene, single-walled carbon nanotubes, multi-walled carbon nanotubes, oxidized carbon nanotubes, and redox carbon nanotubes.
It should be noted that the carbon-based material functions as a reducing agent and may additionally form a conductive network, and thus, in principle, all existing carbon-based materials may be used in the present application.
Preferably, the molar ratio of the carbon-based material to the potassium permanganate is 0.5-3.
Preferably, the preparation method specifically comprises the following steps,
(1) dissolving potassium permanganate in a solvent to prepare a potassium permanganate solution with the concentration of 0.01-0.8 mol/L, and marking the solution A; dispersing a carbon material in the carbon material dispersion liquid to prepare a carbon material solution, and marking the carbon material solution as a solution B;
(2) dropwise adding the solution A into the solution B while stirring to form a uniform mixed solution;
(3) placing the mixed solution obtained in the step (2) at a high temperature of 80-240 ℃ for reacting for 6-72 h to obtain nano powder particles;
(4) separating, washing and drying the nano powder particles obtained in the step (3) to obtain the manganese oxide anode material;
the potassium permanganate-dissolved solvent is deionized water, n-butyl alcohol, a first mixed solution, ethylene glycol or a second mixed solution, wherein the first mixed solution is a mixed solution of the deionized water and the n-butyl alcohol, and the second mixed solution is a mixed solution of the deionized water and the ethylene glycol; the carbon material dispersion liquid is deionized water, dodecyl trimethyl ammonium bromide, ethylenediamine or polyethylene glycol.
Preferably, the preparation method further comprises the step of adjusting the pH value of the mixed solution in the step (2) to 0-5 by using a dilute acid solution with the concentration of 2-20 vol% before the step (3), and then performing the high-temperature hydrothermal reaction in the step (3).
It should be noted that the adjustment of the pH value of the mixed solution can be performed as required, and if the pH value of the mixed solution can meet the reaction requirement of the high-temperature hydrothermal method, the adjustment of the pH value by using a dilute acid solution is not required; the hydrothermal reaction is preferably carried out under acidic conditions, so that the pH value is preferably adjusted by using a dilute acid solution.
Preferably, the dilute acid solution is at least one of dilute sulfuric acid, dilute hydrochloric acid, dilute nitric acid, dilute phosphoric acid and dilute acetic acid.
It should be noted that the dilute acid solution is used to adjust the pH, but in consideration of the influence on the reaction of the high-temperature hydrothermal method, dilute sulfuric acid, dilute hydrochloric acid, dilute nitric acid, dilute phosphoric acid, or dilute acetic acid is preferably used in the present application.
Preferably, the pH value of the dilute acid solution is 0-5.
Preferably, the addition amount of the dilute acid solution is 0-10 mL per 100mL of the mixed solution.
Preferably, in the preparation method of the present application, the step (3) specifically includes pouring the mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, and performing a high-temperature hydrothermal reaction in a constant-temperature air-blast oven.
Preferably, in the preparation method of the present application, the washing in step (4) employs deionized water and ethanol.
Preferably, in the preparation method, the drying in the step (4) is performed by a vacuum oven at 60-120 ℃ for 6-24 h.
The beneficial effect of this application lies in:
the manganese oxide cathode material of the application is characterized in that H is embedded into manganese oxide in situ in the form of Mn-OH + The structure of the manganese oxide can be stabilized. During charging and discharging, H + The manganese oxide positive electrode material and metal ions are cooperatively embedded or separated in the manganese oxide material, so that the manganese oxide positive electrode material has higher capacity, better stability and excellent electrochemical stability; and, at high magnification H + The intercalation or deintercalation of (a) can promote capacity exertion, so that the manganese oxide cathode material of the present application has excellent rate performance.
Drawings
FIG. 1 shows MnO obtained by hydrothermal reaction in the present application 2 H x (H 2 O) y A crystal structure diagram of the positive electrode material particles;
FIG. 2 shows MnO obtained by hydrothermal reaction in example one of the present application 2 H x (H 2 O) y Scanning electron micrographs of the positive electrode material particles;
FIG. 3 shows MnO obtained by hydrothermal reaction in example one of the present application 2 H x (H 2 O) y Transmission electron micrographs of the positive electrode material particles;
FIG. 4 shows MnO obtained by hydrothermal reaction in example one of the present application 2 H x (H 2 O) y A charge-discharge curve of the positive electrode material;
FIG. 5 shows MnO obtained by hydrothermal reaction in example one of the present application 2 H x (H 2 O) y A rate curve of the positive electrode material;
FIG. 6 shows MnO obtained by hydrothermal reaction in example one of the present application 2 H x (H 2 O) y Cycle performance curve of the positive electrode material;
FIG. 7 shows MnO obtained by hydrothermal reaction in example one of the present application 2 H x (H 2 O) y Cathode material H + And Zn 2+ Mechanism of cooperative intercalation or deintercalation.
Detailed Description
The carbon-based material is adopted as a reducing agent for the development of the application, so that the potassium permanganate and the carbon-based material are added into the acidic electrolyteHigh temperature hydrothermal reaction to synthesize MnO in one step 2 H x (H 2 O) y The manganese oxide positive electrode material for an aqueous battery. In one implementation of the present application, the manganese oxide positive electrode material is 1M ZnSO 4 +0.2M MnSO 4 The electrolyte has high capacity, high cycle stability and high rate performance. These excellent electrochemical properties are derived from the particular crystal structure of the manganese oxide positive electrode material of the present application, and during the charge-discharge cycle, taking an aqueous zinc ion battery as an example, as shown in fig. 7, H + And Zn 2+ The structure is synergistically inserted or extracted, and the crystal structure is very stable without generation of a second phase. In addition, the preparation method of the manganese oxide cathode material has the advantages of mild conditions, low cost, high yield and capability of preparing MnO 2 H x (H 2 O) y The manganese oxide positive electrode material has uniform and fine particles and excellent electrochemical performance, and lays a foundation for preparing high-quality water-based batteries.
The present application will be described in further detail with reference to specific examples. The following examples are intended to be illustrative of the present application only and should not be construed as limiting the present application.
Example one
The preparation method comprises the following steps of reducing potassium permanganate into manganese oxide by using an acetylene black carbon-based material as a reducing agent and adopting a high-temperature hydrothermal method, so as to obtain the manganese oxide anode material of the embodiment:
(1) weighing 0.79g of potassium permanganate, dissolving in 30mL of solvent, and uniformly stirring to form a purple clear solution, which is marked as solution A; and weighing 0.06g of acetylene black treated by nitric acid, adding the acetylene black into 30mL of carbon material dispersion liquid, magnetically stirring for 30min, and ultrasonically dispersing for 10min to finally obtain suspension B. Wherein, the solvent is deionized water, n-butanol, glycol, deionized water n-butanol mixed solution or deionized water glycol mixed solution, and the example specifically adopts deionized water; the carbon material dispersion liquid is deionized water, dodecyl trimethyl ammonium bromide, ethylenediamine or polyethylene glycol, and the deionized water is specifically adopted in the embodiment.
(2) Dropwise adding the solution A into the solution B while stirring, adding 2mL of dilute acid solution with the concentration of 10 vol%, magnetically stirring for 30min, and performing ultrasonic dispersion for 10min to obtain a mixed solution. Wherein the dilute acid solution is dilute sulfuric acid, dilute hydrochloric acid, dilute nitric acid, dilute phosphoric acid or dilute acetic acid, and the dilute sulfuric acid is adopted in the embodiment.
(3) And transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining and the volume of which is 100mL, and performing hydrothermal treatment at 120 ℃ for 24 hours to obtain black powder, namely nano powder particles.
(4) And carrying out suction filtration on the black powder obtained by the hydrothermal reaction, cleaning the black powder by using deionized water and ethanol, and drying the black powder for 12 hours at 70 ℃ in a vacuum environment to finally obtain black powder, namely the manganese oxide cathode material.
The manganese oxide positive electrode material prepared in this example was observed by a scanning electron microscope and a transmission electron microscope, respectively, and the results are shown in fig. 2 and fig. 3, where fig. 2 is a scanning electron microscope image and fig. 3 is a transmission electron microscope image. The results of fig. 2 and 3 show that the obtained manganese oxide positive electrode material has a nano petal-shaped morphology, and the nano petal size is about 250 nm; meanwhile, the product obtained by observing the product by a high-resolution transmission electron microscope is a triclinic crystal system, and the lattice spacing of (002) and (020) is determined to be 0.240nm and 0.261nm respectively.
And (3) performance testing:
weighing the materials according to the weight ratio of the manganese oxide anode material to the acetylene black to the PVDF being 70:20:10, and uniformly mixing to prepare slurry; then, the coating is uniformly coated on the stainless steel foil; and after vacuum drying, punching into a circular pole piece. Using metal zinc foil as cathode, 1M ZnSO 4 +0.2M MnSO 4 The mixed solution is used as electrolyte, and the cellulose membrane is used as a diaphragm to form a 2032 button cell.
The charge and discharge performance, the rate capability and the cycle performance of the manganese oxide anode material of the embodiment are tested through a constant current charge and discharge test in a charge and discharge interval of 1.8-1.0V, and the test results are shown in fig. 4-6. Fig. 4 is a charge-discharge curve, fig. 5 is a rate curve, and fig. 6 is a cycle performance curve, in this example, the capacity retention rate of 2000 cycles under 6C condition was tested. The results of fig. 4 to 6 show that the manganese oxide positive electrode material of this example exhibits very high electrochemical performance, 0.1C (1C-308 mAhg) -1 ) Reversible under currentThe charging and discharging capacity is 276mAhg -1 115mAhg still at 10C -1 The capacity of (3), after 2000 cycles under the 6C condition, the capacity retention rate was 79%. The manganese oxide cathode material prepared by the method has high capacity and cycling stability and excellent rate performance.
Example two
In the embodiment, a multiwalled carbon nanotube-based material is used as a reducing agent, and potassium permanganate is reduced into manganese oxide by a high-temperature hydrothermal method, so that the manganese oxide anode material of the embodiment is obtained, and the preparation method comprises the following steps:
(1) weighing 0.79g of potassium permanganate, dissolving in 30mL of deionized water, and uniformly stirring to form a purple clear solution, which is marked as solution A; weighing 0.18g of multi-walled carbon nanotube treated by nitric acid, adding the multi-walled carbon nanotube into 30mL of deionized water, adding 0.1g of dodecyl trimethyl ammonium bromide (CTAB), magnetically stirring for 30min, and ultrasonically dispersing for 10min to finally obtain a suspension B.
(2) Dropwise adding the solution A into the solution B while stirring, magnetically stirring for 30min, and ultrasonically dispersing for 10min to obtain a mixed solution.
(3) And transferring the mixed solution into a 100mL reaction kettle with a polytetrafluoroethylene lining, and performing hydrothermal treatment at 120 ℃ for 24 hours to obtain black powder, namely nano powder particles.
(4) And carrying out suction filtration on the black powder obtained by the hydrothermal reaction, cleaning the black powder by using deionized water and ethanol, and drying the black powder for 12 hours at 70 ℃ in a vacuum environment to finally obtain black powder, namely the manganese oxide cathode material.
The manganese oxide anode material prepared in the example is observed by respectively adopting a scanning electron microscope and a transmission electron microscope, and the result shows that the obtained product is also in a nanometer petal-shaped structure, and the size of the nanometer petal is about-300 nm. High resolution TEM results also show the lattice structure characteristics of triclinic.
And (3) performance testing:
weighing the materials according to the weight ratio of manganese oxide anode material to acetylene black to PVDF being 70:20:10, uniformly mixing to prepare slurry, and uniformly coating the slurry on a stainless steel foil; and after vacuum drying, punching into a circular pole piece. With metallic zincFoil as negative electrode, 3M ZnSO 4 +0.2M MnSO 4 The mixed solution is used as electrolyte, and the cellulose membrane is used as a diaphragm to form a 2032 button cell.
The results of constant current charge and discharge tests in a charge and discharge interval of 1.8 to 1.0V show that the manganese oxide positive electrode material of the embodiment has very high electrochemical performance, and 0.1C (1C is 308 mAhg) -1 ) The reversible charging and discharging capacity under current is 286mAhg -1 Still have 102mAhg at 10C current -1 The capacity of (2), after 300 cycles under the 1C condition, the capacity retention rate was 91%. The manganese oxide cathode material prepared by the method has high capacity and cycling stability and excellent rate performance.
EXAMPLE III
In this example, the manganese oxide positive electrode material prepared in example one was used for H in the manganese oxide positive electrode material + And Na + The synergistic intercalation/deintercalation was tested and verified as follows:
and (3) performance testing:
weighing the materials according to the weight ratio of the manganese oxide positive electrode material to the acetylene black to the PVDF being 70:20:10, and uniformly mixing to prepare slurry; then, the coating was uniformly applied to a stainless steel foil. In a three-electrode system, a metal platinum wire is used as a counter electrode, a stainless steel slurry-coated pole piece is used as a positive electrode, Ag/AgCl is used as a reference electrode, and 1MNa 2 SO 4 +0.2M MnSO 4 The mixed solution is used as electrolyte for electrochemical test.
The charge and discharge performance, the rate capability and the cycle performance of the manganese oxide anode material in the embodiment are tested by a constant-current charge and discharge test of 0.7-0.1V vsAg/AgCl in a charge and discharge interval. The test results show that the manganese oxide cathode material of the present example is 1M Na 2 SO 4 +0.2M MnSO 4 Solution and 0.2M MnSO 4 In solution, 0.1C (1C ═ 308 mAhg) -1 ) The reversible charging and discharging capacity under current is 257mAhg respectively -1 And 132mAhg -1 While Na is found + And H + The intercalation/deintercalation exists in the whole charging and discharging process. Illustrating the positive electrode material of manganese oxide prepared in this example is H during the charging and discharging process + And Na + Can be embedded in cooperationAnd (6) removing.
Example four
In this example, the manganese oxide positive electrode material prepared in example one was used for H in the manganese oxide positive electrode material + And Mg 2+ The synergistic intercalation/deintercalation was tested and verified as follows:
and (3) performance testing:
weighing the materials according to the weight ratio of the manganese oxide anode material to the acetylene black to the PVDF being 70:20:10, and uniformly mixing to prepare slurry; then, the coating was uniformly applied to a stainless steel foil. In a three-electrode system, a metal platinum wire is used as a counter electrode, a stainless steel pole piece coated with slurry is used as a positive electrode, Ag/AgCl is used as a reference electrode, and 2M MgSO 2 4 +0.2M MnSO 4 Solution and 0.2M MnSO 4 The solution was used as an electrolyte for electrochemical testing.
The charge and discharge performance, the rate capability and the cycle performance of the manganese oxide anode material in the embodiment are tested by a constant-current charge and discharge test of 0.7-0.1V vsAg/AgCl in a charge and discharge interval. The test results showed that the manganese oxide positive electrode material of this example was at 2M MgSO 4 +0.2M MnSO 4 Solution and 0.2M MnSO 4 In solution, 0.1C (1C ═ 308 mAhg) -1 ) The reversible charging and discharging capacity under current is 265mAhg -1 And 132mAhg -1 While discovering Mg 2+ And H + The intercalation/deintercalation exists in the whole charging and discharging process. Illustrating the positive electrode material of manganese oxide prepared in this example is H during the charging and discharging process + And Mg 2+ Can be inserted/removed cooperatively.
EXAMPLE five
In this example, the manganese oxide positive electrode material prepared in example one was used for H in the manganese oxide positive electrode material + And Al 3+ The synergistic intercalation/deintercalation was tested and verified as follows:
and (3) performance testing:
weighing the materials according to the weight ratio of the manganese oxide positive electrode material to the acetylene black to the PVDF being 70:20:10, and uniformly mixing to prepare slurry; then, the coating was uniformly applied to a stainless steel foil. In a three-electrode system, the stainless steel is coated with a slurry using a platinum wire as the counter electrodePole piece as positive electrode, Ag/AgCl as reference electrode, 1MAL 2 (SO 4 ) 3 +0.2M MnSO 4 Solution and 0.2M MnSO 4 The solution was used as an electrolyte for electrochemical testing.
The charge and discharge performance, the rate capability and the cycle performance of the manganese oxide anode material in the embodiment are tested by a constant-current charge and discharge test of 0.7-0.1V vsAg/AgCl in a charge and discharge interval. The test results show that the manganese oxide cathode material of the embodiment is 1MAL 2 (SO 4 ) 3 +0.2M MnSO 4 Solution and 0.2M MnSO 4 In solution, 0.1C (1C ═ 308 mAhg) -1 ) The reversible charging and discharging capacity under current is 239mAhg respectively -1 And 132mAhg -1 While Al is found 3+ And H + The intercalation/deintercalation exists in the whole charging and discharging process. Illustrating the positive electrode material of manganese oxide prepared in this example is H during the charging and discharging process + And Al 3+ Can be inserted/removed cooperatively.
EXAMPLE six
In this example, the manganese oxide positive electrode material prepared in example one was used for H in the manganese oxide positive electrode material + And K + The synergistic intercalation/deintercalation was tested and verified as follows:
and (3) performance testing:
weighing the materials according to the weight ratio of the manganese oxide positive electrode material to the acetylene black to the PVDF being 70:20:10, and uniformly mixing to prepare slurry; then, the coating was uniformly applied to a stainless steel foil. In a three-electrode system, a platinum wire is used as a counter electrode, a stainless steel slurry-coated pole piece is used as a positive electrode, Ag/AgCl is used as a reference electrode, 1M K 2 SO 4 +0.2M MnSO 4 The mixed solution is used as electrolyte for electrochemical test.
The charge and discharge performance, the rate capability and the cycle performance of the manganese oxide anode material in the embodiment are tested by a constant-current charge and discharge test of 0.7-0.1V vsAg/AgCl in a charge and discharge interval. The test results show that the manganese oxide cathode material of the embodiment shows very high electrochemical performance, and K is found + And H + The intercalation/deintercalation exists in the whole charging and discharging process. The manganese oxide prepared in this example is illustratedDuring the charge and discharge of the anode material, H + And K + Can be inserted/removed cooperatively.
The foregoing is a more detailed description of the present application in connection with specific embodiments thereof, and it is not intended that the present application be limited to the specific embodiments thereof. It will be apparent to those skilled in the art from this disclosure that many more simple deductions or substitutions can be made without departing from the spirit of the disclosure.
Claims (14)
1. A manganese oxide positive electrode material for an aqueous battery, characterized in that: the molecular formula of the manganese oxide anode material is MnO 2 H x (H 2 O) y Wherein x is more than 0 and less than 1, and y is more than 0 and less than 1;
during charging and discharging, the manganese oxide is embedded with H + And metal ions, H + In the form of Mn-OH, metal ions in the form of Mn-O-metal ions, and H + And metal ions are removed or inserted in the manganese oxide anode material in a synergistic way;
the metal ions at least contain Zn 2+ 。
2. The manganese oxide positive electrode material according to claim 1, characterized in that: the metal ions further contain Li + 、Na + 、K + 、Mg 2+ And Al 3+ At least one of (1).
3. The manganese oxide positive electrode material according to claim 1, characterized in that: the manganese oxide positive electrode material is a nanoparticle, a nanowire or a nanosheet;
the thickness of the nanosheet is 1-10 nm, and the diameter of the nanosheet is 200-800 nm.
4. Use of the manganese oxide positive electrode material according to any one of claims 1 to 3 in an aqueous battery which is a primary battery or a secondary battery;
the water system battery is a zinc ion battery, a lithium ion battery, a sodium ion battery, a potassium ion battery, a magnesium ion battery or an aluminum ion battery.
5. An aqueous primary battery or an aqueous secondary battery using the manganese oxide positive electrode material according to any one of claims 1 to 3.
6. Use of the water-based primary battery or the water-based secondary battery according to claim 5 in energy storage, 3C electronic products, or new energy electric vehicles;
the 3C electronic product comprises a mobile phone, a notebook computer and a tablet computer.
7. The method for producing a manganese oxide positive electrode material according to any one of claims 1 to 3, characterized in that: the method comprises the steps of adopting a high-temperature hydrothermal method, taking potassium permanganate and a carbon-based material as reactants, and synthesizing the manganese oxide anode material in one step; the reaction temperature of the high-temperature hydrothermal method is 80-240 ℃, and the reaction time is 6-72 h;
the carbon-based material is at least one of charcoal, carbon black, carbon cloth, carbon paper, carbon fiber, acetylene black, SP, KS6, graphite, graphene oxide, redox graphene, single-walled carbon nanotubes, multi-walled carbon nanotubes, oxidized carbon nanotubes and redox carbon nanotubes;
the molar ratio of the carbon-based material to the potassium permanganate is 0.5-3;
the method specifically comprises the following steps of,
(1) dissolving potassium permanganate in a solvent to prepare a potassium permanganate solution with the concentration of 0.01-0.8 mol/L, and marking the solution A; dispersing a carbon material in the carbon material dispersion liquid to prepare a carbon material solution, and marking the carbon material solution as a solution B;
(2) dropwise adding the solution A into the solution B while stirring to form a uniform mixed solution;
(3) placing the mixed solution obtained in the step (2) at a high temperature of 80-240 ℃ for reaction for 6-72 h to obtain nano powder particles;
(4) separating, washing and drying the nano powder particles obtained in the step (3) to obtain the manganese oxide anode material;
the potassium permanganate-dissolved solvent is deionized water, n-butyl alcohol, a first mixed solution, ethylene glycol or a second mixed solution, wherein the first mixed solution is a mixed solution of the deionized water and the n-butyl alcohol, and the second mixed solution is a mixed solution of the deionized water and the ethylene glycol;
the carbon material dispersion liquid is deionized water, dodecyl trimethyl ammonium bromide, ethylenediamine or polyethylene glycol.
8. The method of claim 7, wherein: and (3) before the step (3), adjusting the pH value of the mixed solution in the step (2) to 0-5 by using a dilute acid solution with the concentration of 2-20 vol%, and then carrying out the high-temperature hydrothermal reaction in the step (3).
9. The method of claim 8, wherein: the dilute acid solution is at least one of dilute sulfuric acid, dilute hydrochloric acid, dilute nitric acid, dilute phosphoric acid and dilute acetic acid.
10. The method of claim 8, wherein: the pH value of the dilute acid solution is 0-5.
11. The method for producing according to claim 8, characterized in that: the addition amount of the dilute acid solution is 0-10 mL of the dilute acid solution per 100mL of the mixed solution.
12. The method of claim 8, wherein: and (3) pouring the mixed solution into a hydrothermal reaction kettle with a polytetrafluoroethylene lining, and carrying out high-temperature hydrothermal reaction in a constant-temperature air-blast oven.
13. The method of claim 8, wherein: in the step (4), deionized water and ethanol are adopted for washing.
14. The method of claim 8, wherein: in the step (4), the drying is carried out for 6-24 hours at 60-120 ℃ by adopting a vacuum oven.
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| CN107863485A (en) * | 2017-11-06 | 2018-03-30 | 中南大学 | A kind of water system Zinc ion battery positive electrode |
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| CN107863485A (en) * | 2017-11-06 | 2018-03-30 | 中南大学 | A kind of water system Zinc ion battery positive electrode |
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