CN115117468A - Birnessite type delta-MnO for improving zinc electricity of water system 2 Electrolyte with positive polarity and preparation method thereof - Google Patents
Birnessite type delta-MnO for improving zinc electricity of water system 2 Electrolyte with positive polarity and preparation method thereof Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 83
- 239000011701 zinc Substances 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000005611 electricity Effects 0.000 title claims abstract description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000007774 positive electrode material Substances 0.000 claims abstract description 15
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- 238000010438 heat treatment Methods 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
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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
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
- H01M2300/0011—Sulfuric acid-based
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Abstract
The invention belongs to the technical field of water-system zinc ion batteries, and particularly relates to a method for improving zinc electricity Birnessite type delta-MnO of a water system 2 Electrolyte with positive electrode material performance and a preparation method thereof. The invention directly adopts solvent NMP for preparing the current collector, and adds a small amount of NMP into ZnSO 4 Preparing cheap electrolyte, and using cheap, safe and environment-friendly gamma-MnO 2 Uses a simple hydrothermal method to prepare K as a raw material + Pre-embedded delta-MnO 2 As the active material of the positive electrode of the battery and the zinc sheet as the negative electrode of the battery, the manufactured battery has excellent electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of water-system zinc ion batteries, and particularly relates to a method for improving the zinc Birnessite type delta-MnO of a water system 2 An electrolyte with the performance of a positive electrode material, a preparation method thereof and application thereof in an aqueous zinc ion battery.
Background
The rechargeable water-based zinc ion battery is a novel secondary battery which is started in recent years, and has the characteristics of high energy density, high power density, non-toxic battery materials, low price, simple preparation process and the like. The water system zinc ion battery mainly comprises a positive electrode, a negative electrode, a current collector, a diaphragm and electrolyte. Currently, the development of aqueous zinc ion energy storage batteries has mostly focused on electrode materials. Yuan et al uses LiMn 2 O 4 And H 2 SO 4 As raw materialSynthesizing lambda-MnO 2 The anode is 1M ZnSO 4 The maximum discharge capacity of the solution is 33.64mAh g -1 (Current Density: 408mA g -1 ). Han et al use beta-MnO 2 As cathode, electrolyte is 3M ZnSO 4 And 0.1M MgSO 4 Mixed solution, 50mAg -1 The maximum discharge capacity at the current density was 302mAh g -1 . Mathew et al prepared gamma-MnO by high temperature annealing 2 Cathode and electrolyte are 1M ZnSO 4 The maximum discharge capacity is 285mAh g -1 (Current Density: 2.46mA g -1 ) At 24.6mA g -1 57.8% of the discharge capacity remained after 50 cycles of charge and discharge at the current density. It is obvious that Zn is changed by the design of simple and efficient electrolyte 2+ Kinetic methods are also rare. The conventional electrolyte design idea is that high-concentration metal salt or organic matter and other additives are added into the electrolyte, so that the stability of the Zn surface can be effectively improved, for example, Gao and other people add 2M ZnSO 4 And 0.1M MnSO 4 Adding a large amount of attapulgite nano inorganic material into the solution to prepare colloid electrolyte which is prepared from alpha-MnO 2 As a cathode of the battery, the discharge capacity after 1000 times of charge and discharge cycles was kept at 89% (current density: 500mA g) -1 ). However, the high concentration of the electrolyte additive increases the probability of side reactions, affects the diffusion kinetics of zinc ions, and increases the cost, and the high concentration of the organic additive also creates a safety hazard, which is contrary to the original design concept of the aqueous zinc battery. Therefore, there remains a need to explore the use of inexpensive and low-concentration electrolyte additives.
The research and development of the preparation technology of the water-based zinc ion battery mainly focuses on preparing battery electrode materials at present, and the adopted conventional electrolyte is usually 2mol L -1 ZnSO 4 Mainly, 0.1mol L of the catalyst is properly added -1 MnSO 4 And 0.1mol L -1 K 2 SO 4 . For example, Birnessite type delta-MnO 2 As a material with a laminated structure, the interlayer distance is 0.7nm, and compared with the alpha-MnO which is researched more at present 2 Theoretically, it is more suitable for the storage and release of zinc ions, however, delta-MnO 2 The layered structure is easy to be damaged in the charging and discharging process, and 2mol L of the layered structure is adopted -1 ZnSO 4 The electrolyte mainly generates solvation sheath effect to cause Zn 2+ The dynamic performance is deteriorated, the polarization effect of water is strong, and Zn is also affected 2+ The kinetic properties are adversely affected and the diffusion of ions in the material matrix is adversely affected, leading to poor cycling stability and rate performance.
However, the general idea is that adding inorganic electrolyte solute with high concentration increases the cost, and adding organic electrolyte solute with high concentration not only increases the cost, but also increases the potential safety hazard.
In industrial production and laboratory development, before an active material coated on a current collector of a battery electrode is manufactured, the active material and a binder are mixed by using relatively cheap n-methyl-2-pyrrolidone (NMP) with a purity of 99.9% as a solvent and then coated on the current collector. The invention directly adopts solvent NMP for preparing the current collector, and adds a small amount of NMP into ZnSO 4 The solution (NMP addition amount accounts for 4-8% of the total electrolyte volume percent) is used for preparing the cheap electrolyte, and the cheap, safe and environment-friendly gamma-MnO is adopted 2 Uses a simple hydrothermal method to prepare K as a raw material + Pre-embedded delta-MnO 2 As a battery positive electrode (K) + Pre-embedding to prevent structural collapse of electrode materials in the charge and discharge process), and assembling a button cell to evaluate by using a zinc sheet as a cell cathode. Therefore, NMP is added by a simple method to prepare the electrolyte with excellent performance.
Disclosure of Invention
The invention directly adopts solvent NMP for preparing the current collector, and adds a small amount of NMP into ZnSO 4 The solution (NMP addition accounts for 4-8% of the total volume of the electrolyte) is used for preparing the cheap electrolyte, and the cheap, safe and environment-friendly gamma-MnO is matched for use 2 Uses a simple hydrothermal method to prepare K as a raw material + Pre-embedded delta-MnO 2 As a battery positive electrode (K) + Pre-embedding to prevent structural collapse of electrode materials in the charge and discharge process), and assembling a button cell to evaluate by using a zinc sheet as a cell cathode. This patent adoptsNMP is added in a simple method to prepare the electrolyte with excellent performance and suitable for the battery anode.
An electrolyte for improving the positive polarity of aqueous zinc-electricity Birnessite type delta-MnO 2 is prepared by configuring ZnSO 4 Adding a certain amount of NMP into the solution to obtain the solution; wherein the NMP accounts for 4-8% of the total electrolyte by volume percent.
Further, ZnSO 4 The solution is prepared by deionized water, and the concentration is preferably 1-3mol L -1 More preferably 2mol L -1 。
The method for improving the zinc electricity Birnessite type delta-MnO of the water system 2 The electrolyte with positive polarity is applied to an aqueous zinc ion battery.
The water-based zinc ion battery comprises the electrolyte, and the positive electrode material of the battery is K matched with the electrolyte for use + Pre-embedded delta-MnO 2 。
The preparation method of the battery anode material comprises the following steps: taking gamma-MnO 2 Mixing with KOH solution and carrying out hydrothermal reaction under heat preservation, wherein the gamma-MnO is 2 And KOH in a mass ratio of 0.5 to 0.6: 1; collecting reaction products, washing and drying to obtain delta-MnO pre-embedded with K + 2 Denoted as KMO.
Preferably, the temperature of the anode material hydrothermal reaction step is 150-170 ℃, and the reaction time is 60-80 h; the temperature of the drying step is 70-100 ℃, and the heating treatment is carried out for 1.5-3 h. Further preferably, the temperature of the anode material hydrothermal reaction step is 160 ℃, and the reaction time is 72 h; the temperature of the drying step is 70 ℃, and the heating treatment is carried out for 2 h.
The preparation method of the water-based zinc ion battery comprises the following steps: mixing the positive electrode material, acetylene black and polyvinylidene fluoride according to a certain mass ratio, putting the mixture into an agate mortar, dripping N-methyl-2-pyrrolidone (NMP), grinding and mixing to prepare positive electrode slurry, coating the positive electrode slurry on a stainless steel mesh current collector, drying in an oven, and assembling the positive electrode current collector, a glass fiber diaphragm, a zinc foil negative electrode and an electrolyte to obtain the battery.
Wherein the mass of the anode material, the acetylene black and the polyvinylidene fluorideThe ratio is 6-8: 1-3: 0.5 to 1.5, and preferably 7: 2: 1, the loading capacity of the anode slurry is 1.8-2.2mg cm -2 The oven conditions are preferably: drying at 70-100 deg.C for 6-10h in air environment. The assembled battery is preferably a button battery, and is more preferably a CR2032 button battery.
Specifically, the technical scheme of the invention is as follows:
preparing ZnSO with deionized water 4 The NMP accounts for 4-8% of the total electrolyte volume, and cheap nontoxic gamma-MnO is adopted 2 Uses a simple hydrothermal method to prepare K as a raw material + Pre-embedded delta-MnO 2 And (4) as a positive electrode, and a zinc sheet as a negative electrode, and manufacturing a button cell for testing.
For example, the preparation method of the anode material of the water-based zinc ion battery comprises the following steps: Gamma-MnO 2 And KOH in a mass ratio of 0.5 to 0.6: 1, taking gamma-MnO 2 Mixing with KOH solution, and carrying out hydrothermal reaction under the condition of heat preservation, wherein the temperature of the step of hydrothermal reaction is 150-170 ℃, the reaction time is 60-80h, and the reaction time is preferably 160 ℃ for 72 h; collecting the reaction product, washing and drying, wherein the temperature of the drying step is 70-100 ℃ for heating treatment for 1.5-3h, preferably 70 ℃ for heating for 2h for drying. Obtaining the Pre-Embedded K + delta-MnO of 2 Marked as KMO for standby; the preparation method of the electrolyte comprises the following steps: preparing 2mol L of deionized water -1 ZnSO 4 The solutions were added with different amounts of NMP (e.g., electrolyte sample numbers: N0, N3, N4, N6, N8, N9, N30 indicate NMP in 0%, 3%, 4%, 6%, 8%, 9%, 30%, respectively, of the total volume of the electrolyte).
Mixing the positive electrode material KMO, acetylene black and polyvinylidene fluoride (PVDF) according to a certain mass ratio (for example, mixing at a mass ratio of 7: 2: 1 and corresponding to 0.07 g: 0.02 g: 0.01g), putting into an agate mortar, dripping 0.3-0.5 ml of n-methyl-2-pyrrolidone, grinding and mixing to prepare positive electrode slurry, coating the positive electrode slurry on a stainless steel mesh current collector with the diameter of 14mm by using a soft blade, drying for 6-10h at 70-100 ℃ in an oven under an air environment, wherein the load of the positive electrode slurry is 1.8-2.2mg cm -2 The positive current collector, the glass fiber diaphragm, the zinc foil negative electrode and 0.2-0.25ml of electrolyte are filled into the CR2032 button cell.
A LAND CT2001A type measuring instrument is adopted to test the battery activation, discharge capacity, cycle performance, high rate performance and energy density, and test results show that when the NMP addition amount accounts for 4-8% of the total electrolyte volume percentage, the battery has very excellent electrical properties.
The invention directly adopts a solvent NMP for preparing a current collector, and a small amount of NMP is added into 2mol L -1 ZnSO 4 (NMP accounts for 4-8% of the total electrolyte volume percent) to prepare cheap electrolyte; meanwhile, as for the preparation of the positive electrode, cheap nontoxic gamma-MnO is adopted 2 Uses a simple hydrothermal method to prepare K as a raw material + Pre-embedded delta-MnO 2 ，K + Pre-embedded delta-MnO 2 The layered structure expands the zinc storage channel of the material, improves the structural stability of the material, and avoids the rapid capacity attenuation caused by the collapse of the layered structure due to the embedding/separating of zinc ions in the circulation process.
For the electrolyte, Zn without addition of NMP 2+ The surrounding usually contains a certain number (less than or equal to 6) of water molecules of solvation, which is unfavorable for Zn 2+ The dynamic performance of the device is improved; when adding NMP, Zn 2+ Partial surrounding solvated water molecules are replaced by NMP, alleviating Zn 2+ The water solvation of the water improves the dynamic performance of the water. Therefore, the addition of a small amount of NMP helps to promote Zn 2+ Migration and diffusion between KMO anode material layers.
The invention has the beneficial effects that:
according to the electrolyte prepared by the invention, the NMP is a solvent for preparing the current collector, but not other valuable organic additives, so that the cost is relatively low, the electrolyte is practical, and the addition amount of the NMP is small (the addition amount of the NMP accounts for 4-8% of the total volume of the electrolyte), so that the electrolyte is safe and environment-friendly; the raw material for preparing the anode is gamma-MnO 2 which is cheap, safe and environment-friendly, and is not the traditional toxic controlled medicine KMnO 4 (ii) a A simple hydrothermal method is adopted; the preparation technology is suitable for large-scale production and amplification.
Drawings
In order to more clearly illustrate the embodiments of the present application or technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings can be obtained by those skilled in the art according to the drawings.
Wherein the content of the first and second substances,
FIG. 1 is an XRD spectrum of KMO prepared in example;
FIG. 2 is Raman spectra of N0, N3, N6, N9 and N30(NMP is added in an amount of 0%, 3%, 6%, 9% and 30% of the total electrolyte volume percentage);
FIG. 3 shows that the KMO-based button cell is formed at 100mA g when NMP is added in an amount of 0% by volume of the total electrolyte -1 Discharge capacity-voltage curve graph of 10 th circle under current density;
FIG. 4 shows the KMO-based coin cell at 100mA g when NMP was added in an amount of 3% by volume based on the total electrolyte -1 Discharge capacity-voltage curve graph of 10 th circle under current density;
FIG. 5 shows the KMO-based coin cell at 100mA g when NMP was added in an amount of 4% by volume based on the total electrolyte -1 Discharge capacity-voltage curve graph of 10 th circle under current density;
FIG. 6 shows that the KMO-based button cell is operated at 100mA g/g when NMP is added in an amount of 6% by volume based on the total electrolyte -1 Discharge capacity-voltage curve graph of 10 th circle under current density;
FIG. 7 shows that the KMO-based button cell is operated at 100mA g/g when NMP is added in an amount of 8% by volume of the total electrolyte -1 Discharge capacity-voltage curve graph of 10 th circle under current density;
FIG. 8 shows that the KMO-based button cell is operated at 100mA g/g when NMP is added in an amount of 9% by volume of the total electrolyte -1 Discharge capacity-voltage curve graph of 10 th circle under current density;
FIG. 9 shows the KMO-based coin cell at 100mA g when NMP was added at 30% by volume of the total electrolyte -1 The discharge capacity-voltage curve diagram of the 10 th circle under the current density;
FIG. 10 is a graph of rate performance corresponding to NMP addition of 0% by volume of the total electrolyte;
FIG. 11 is a graph of rate performance corresponding to a total electrolyte volume percentage of 3% added NMP;
FIG. 12 is a graph of rate performance corresponding to NMP addition of 4% by volume of the total electrolyte;
FIG. 13 is a graph of rate performance corresponding to a total electrolyte volume percentage of 6% added NMP;
FIG. 14 is a graph of rate performance corresponding to an NMP addition of 8% by volume of the total electrolyte;
FIG. 15 is a graph of rate performance corresponding to a total electrolyte volume percentage of 9% added NMP;
FIG. 16 is a graph of rate performance corresponding to an NMP addition of 30% by volume of the total electrolyte;
FIG. 17 is a graph showing the decay curve of discharge capacity corresponding to 200 cycles when the addition amount of NMP is 0% based on the total volume percentage of the electrolyte;
FIG. 18 is a graph showing the decay of discharge capacity after 2000 cycles when NMP is added in an amount of 0% by volume of the total electrolyte;
FIG. 19 is a graph showing the decay of discharge capacity after 200 cycles when NMP is added in an amount of 3% by volume of the total electrolyte;
FIG. 20 is a graph showing the decay of discharge capacity after 2000 cycles when NMP is added in an amount of 3% by volume of the total electrolyte;
FIG. 21 is a graph showing the decay of discharge capacity after 200 cycles when NMP is added in an amount of 4% by volume of the total electrolyte;
FIG. 22 is a graph showing the decay of discharge capacity after 2000 cycles when NMP is added in an amount of 4% by volume of the total electrolyte;
FIG. 23 is a graph showing the decay of discharge capacity after 200 cycles when the amount of NMP added is 6% by volume of the total electrolyte;
FIG. 24 is a graph showing the decay of discharge capacity after 2000 cycles when the amount of NMP added is 6% by volume of the total electrolyte;
FIG. 25 is a graph showing the decay curve of discharge capacity corresponding to 200 cycles when the total volume percentage of the electrolyte is 8% by adding NMP;
FIG. 26 is a graph showing the decay of discharge capacity after 2000 cycles when NMP is added in an amount of 8% by volume of the total electrolyte;
FIG. 27 is a graph showing the decay of discharge capacity after 200 cycles when NMP is added in an amount of 9% by volume of the total electrolyte;
FIG. 28 is a graph showing the decay of discharge capacity after 2000 cycles when NMP is added in an amount of 9% by volume of the total electrolyte;
FIG. 29 is a graph showing the decay of discharge capacity after 200 cycles when NMP is added in an amount of 30% by volume of the total electrolyte;
fig. 30 is a graph showing the decay of discharge capacity after 2000 cycles of the total electrolyte volume percentage of NMP addition of 30%.
Detailed Description
In order to facilitate an understanding of the invention, various exemplary embodiments of the invention will now be described in detail, which should not be construed as a specific limitation of the invention, but rather as a more detailed description of certain aspects, features and embodiments of the invention.
Example (b): preparing 2mol L of deionized water -1 ZnSO 4 The solution is prepared by adding NMP 4-8 vol%, 4%, 6%, 8% (expressed by N4, N6, N8), and using cheap nontoxic gamma-MnO 2 Uses a simple hydrothermal method to prepare K as a raw material + Pre-embedded delta-MnO 2 And (4) as a positive electrode, and a zinc sheet as a negative electrode, and manufacturing a button cell for testing.
Comparative example: adding NMP in the amount of 0%, 3%, 9%, 30% (expressed as N0, N3, N9, N30) and using cheap nontoxic gamma-MnO 2 Uses a simple hydrothermal method to prepare K as a raw material + Pre-embedded delta-MnO 2 And (4) as a positive electrode, and a zinc sheet as a negative electrode, and manufacturing a button cell for testing.
Specifically, the preparation method of the anode material of the water-based zinc ion battery comprises the following steps: Gamma-MnO 2 And KOH in a mass ratio of 0.5: 1, mixing gamma-MnO 2 with a KOH solution, and carrying out a hydrothermal reaction at the temperature of 160 ℃ for 72 hours under the condition of heat preservation. Collecting reaction products, washing and drying, wherein the temperature of the drying step is 70 ℃, and heating treatment is carried out for 2 hours to obtain delta-MnO of pre-embedded K + 2 Marked as KMO for standby; as shown in FIG. 1, the XRD pattern of KMO prepared from the compound is delta-MnO in comparison with standard PDF card 2 。
The preparation method of the electrolyte comprises the following steps: preparing 2mol L of deionized water -1 ZnSO 4 Adding NMP with different contents into the solution, and numbering the electrolyte samples: n0, N3, N4, N6, N8, N9 and N30 respectively represent NMP accounting for 0%, 3%, 4%, 6%, 8%, 9% and 30% of the total volume of the electrolyte. As shown in the Raman spectrum of FIG. 2, the peak position representing C ═ O vibration was 1650cm -1 In the vicinity, for example, N0, N3, N6, N9 and N30 show a red shift of C ═ O shock peak, indicating 2mol L -1 ZnSO 4 NMP was added to the solution, and as the amount of NMP added, the C ═ O vibration intensity increased, which also confirmed that the NMP content in N0, N3, N6, N9, and N30 increased stepwise.
Electrical Performance testing
Taking the positive electrode material KMO, acetylene black and polyvinylidene fluoride (PVDF), and mixing the materials in a mass ratio of 7: 2: 1 (0.07 g: 0.02 g: 0.01g) is put into an agate mortar, 0.4 ml of N-methyl-2-pyrrolidone is dropped into the mortar, grinding and mixing are carried out to prepare anode slurry, a soft blade is coated on a stainless steel mesh current collector with the diameter of 14mm, drying is carried out for 8 hours at 70 ℃ in an oven under the air environment, and the loading capacity of the anode slurry is 2.0mg cm -2 A positive electrode current collector, a glass fiber diaphragm, a zinc foil negative electrode, and 0.2ml of electrolyte (N0, N3, N4, N6, N8, N9, N30) were charged into a CR2032 coin cell.
A LAND CT2001A type measuring instrument is adopted to test the activation, discharge capacity, cycle performance, high rate performance and energy density of the battery, and the test results are all based on the quality of the positive active material.
a. Discharge capacity test
The method comprises the following steps of respectively testing the discharge capacity of the button cell formed on the basis of the KMO anode material, and specifically comprises the following steps:
step 1: 100mA g -1 Charging to a potential of 1.8V;
step 2: 100mA g -1 Discharging to 0.8V;
and step 3: repeating the steps 1-2 until the discharge capacity of the battery reaches a maximum value (C) max ) The corresponding number is called the activation number (N) a )。
FIGS. 3-9 show the KMO-based button cell at 100mA g -1 Discharge capacity-voltage plot at 10 th cycle at current density.
b. High rate performance test
The method comprises the following steps of respectively carrying out high-rate performance test on the button cell formed on the basis of the positive electrode material KMO, and specifically comprising the following steps:
step 1: 100mA g -1 Charging to a potential of 1.8V;
and 2, step: 100mA g -1 Discharging to 0.8V;
and 3, step 3: repeating the step 1-2 until the charging and discharging times of the battery are 10;
and 4, step 4: 200mA g -1 Charging to a potential of 1.8V;
and 5: 200mA g -1 Discharging to 0.8V;
and 6: repeating the steps 4-5 until the charging and discharging times of the battery are 10;
and 7: 400mA g -1 Charging to a potential of 1.8V;
and 8: 400mA g -1 Discharging to 0.8V;
and step 9: repeating the steps 7-8 until the charging and discharging times of the battery are 10;
step 10: 600mA g -1 Charging to a potential of 1.8V;
step 11: 600mA g -1 Discharging to 0.8V;
step 12: repeating the steps 10-11 until the charging and discharging times of the battery are 10;
step 13: 800mA g -1 Charging to the potential of 1.8V;
step 14: 800mA g -1 Discharging to 0.8V;
step 15: repeating the steps 13-14 until the number of charging and discharging times of the battery is 10;
step 16: 1A g -1 Charging to a potential of 1.8V;
and step 17: 1A g -1 Discharging to 0.8V;
step 18: repeating the steps 16-17 until the number of charging and discharging times of the battery is 10;
step 19: 800mA g -1 Charging to a potential of 1.8V;
step 20: 800mA g -1 Discharging to 0.8V;
step 21: repeating the steps 19-20 until the number of charging and discharging times of the battery is 10;
step 22: 600mAg -1 Charging to a potential of 1.8V;
step 23: 600mA g -1 Discharging to 0.8V;
step 24: repeating the steps 22-23 until the number of charging and discharging times of the battery is 10;
step 25: 400mAg -1 Charging to a potential of 1.8V;
step 26: 400mAg -1 Discharging to 0.8V;
step 27: repeating the steps 25-26 until the number of charging and discharging times of the battery is 10;
step 28: 200mA g -1 Charging to a potential of 1.8V;
step 29: 200mA g -1 Discharging to 0.8V;
step 30: repeating the steps 28-29 until the number of charging and discharging times of the battery is 10;
step 31: 100mA g-1 is charged to the potential of 1.8V;
step 32: discharging 100mA g-1 to 0.8V of potential;
step 33: repeating the steps 31-32 until the number of charging and discharging times of the battery is 10;
the high rate performance test results are shown in table 1 below. FIGS. 10-16 are graphs of rate performance corresponding to N0, N3, N4, N6, N8, N9 and N30. The test results show that N0, N3, N4, N6,N8, N9 and N30 at 100mA g -1 N at current density a All 10, the maximum discharge capacity at this time was: 210.7, 241.6, 311.4, 315.3, 312.5, 278.5, 222.8mA g -1 . The discharge capacities of N4, N6 and N8 are obviously higher under the same discharge current density, and in addition, the discharge capacities of N4, N6 and N8 all exceed 200mAh g under the large current density of 1A/g -1 Compared with comparative examples of N0, N3, N9 and N30, the rate performance has obvious advantages. And for N4, N6 and N8, as the discharge current density is increased from 100mA/g to 1A/g, the discharge capacity is gradually reduced, and as the discharge current density is reduced from 1A/g to 100mA/g, the discharge capacity at each discharge current density is basically close to the discharge capacity at the corresponding current density in the process of increasing the discharge current density from 100mA/g to 1A/g, so that the good reversibility is shown. This demonstrates that a significantly superior effect is exhibited in high rate performance testing when the amount of NMP added is 4-8% by volume of the total electrolyte.
Table 1 high rate performance test results
c. Cycle performance test
Respectively carrying out cycle performance tests on the button cell formed on the basis of the positive electrode material KMO, wherein the cycle performance tests comprise 200 times of cycle tests and 2000 times of cycle tests; wherein:
the test is circulated for 200 times, and the specific steps comprise:
step 1: 100mA g -1 Charging to a potential of 1.8V;
and 2, step: 100mA g -1 Discharging to 0.8V;
and 3, step 3: repeating the steps 1-2 until the charge-discharge cycle reaches 200 times.
Stability usable Capacity Retention ratio (S) in 200 Charge-discharge cycles 200 ) To characterize:
S 200 ＝C 200 /C max
in the formula, C 200 Represents 100mA g -1 Discharge capacity at the next 200 th cycle, C max Represents 100mA g -1 Lower maximum discharge capacity;
fig. 17-30 are discharge capacity decay plots corresponding to 200 and 2000 cycles, respectively. The specific test results are shown in table 2:
it can be seen that at 100mA g -1 Under the discharge current density, the energy density of N4, N6 and N8 is above 420Wh/Kg, the coulombic efficiency is close to 100 percent, and the discharge capacity of the 200 th circle is 270mAh g -1 About, the capacity retention rate at the 200 th turn was 86% or more, and the overall performance was significantly more excellent than those of comparative examples N0, N3, N9, and N30. This demonstrates that when the NMP addition is 4-8% by volume of the total electrolyte, significantly more excellent results are exhibited when 200 cycles of performance testing are performed.
TABLE 2 Performance test results for 200 cycles
| 100mA g -1 | N0 | N3 | N4 | N6 | N8 | N9 | N30 |
| Coulombic efficiency | 95.36％ | 96.63％ | 99.31％ | 99.99％ | 99.54％ | 97.45％ | 95.58％ |
| C200/mAh g -1 | 48.9 | 141.1 | 268.77 | 273.9 | 270.41 | 193.4 | 92.2 |
| S200 | 23.21％ | 58.40％ | 86.31％ | 86.87％ | 86.53％ | 69.44％ | 41.38％ |
| Energy density Wh/Kg | 276.02 | 321.33 | 420.39 | 425.66 | 421.88 | 367.62 | 289.64 |
The test is circulated for 2000 times, and the specific steps comprise:
step 1: 1A g -1 Charging to a potential of 1.8V;
step 2: 1A g -1 Discharging to 0.8V;
and 3, step 3: repeating the steps 1-2 until the charge-discharge cycle reaches 2000 times.
Capacity retention rate (S) for stability of charge-discharge cycle at 2000 times 2000 ) To characterize:
S 2000 ＝C 2000 /C max
in the formula, C 2000 Representation 1A g -1 Discharge capacity at the next 2000 th cycle, C max Representation 1A g -1 The lower maximum discharge capacity. The specific test results are shown in table 3:
TABLE 3 Performance test results for 2000 cycles
| 1A g -1 | N0 | N3 | N4 | N6 | N8 | N9 | N30 |
| C2000/mAh g -1 | 10.00 | 47.50 | 200.2 | 206.4 | 201.5 | 84.10 | 28.70 |
| S2000 | 19.53％ | 63.59％ | 95.15％ | 95.96％ | 95.34％ | 71.33％ | 46.22％ |
Can be seen in 1A g -1 The discharge capacities of the 2000 th circles of N4, N6 and N8 were all 200mAh g under the discharge current density -1 As described above, the capacity retention rate of the 2000 th turn was 95% or more, and the overall performance was significantly more excellent than those of comparative examples N0, N3, N9, and N30. This demonstrates that when the volume percentage of the NMP addition to the total electrolyte is 4-8%, the performance test performed in 2000 cycles still shows significantly more excellent results.
Therefore, the ZnSO prepared by using the deionized water in the invention 4 When NMP accounts for 4-8% of the total electrolyte volume, the solution is matched with cheap and nontoxic gamma-MnO 2 Simple hydrothermal method for preparing K from raw materials + Pre-embedded delta-MnO 2 The button cell prepared by using the zinc sheet as the cathode has good use effect on electrical performance tests such as discharge capacity, high rate performance test, cycle performance test and the like.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The electrolyte for improving the positive performance of the aqueous zinc electrobinnessite type delta-MnO 2 is characterized in that ZnSO is configured in the electrolyte 4 Adding a certain amount of NMP into the solution to obtain the solution;
wherein the NMP accounts for 4-8% of the total electrolyte by volume percent.
2. The method of claim 1 for enhancing zinc electroyield Birnessite-type δ -MnO in an aqueous process 2 Electrolyte of positive polarity, further, ZnSO 4 The solution is prepared by deionized water with the concentration of 1-3mol L -1 。
3. The method as claimed in claim 1 or 2, wherein the zinc-enhanced Birnessite-type delta-MnO is used for improving water system zinc electricity 2 The electrolyte with positive polarity is applied to an aqueous zinc ion battery.
4. An aqueous zinc ion battery comprising the electrolyte solution according to claim 1 or 2, wherein the positive electrode material of the battery is K used in combination with the electrolyte solution + Pre-embedded delta-MnO 2 。
5. The aqueous zinc-ion battery according to claim 4, wherein the preparation method of the battery positive electrode material comprises the following steps: taking gamma-MnO 2 Mixing with KOH solution and carrying out hydrothermal reaction under heat preservation, wherein the gamma-MnO is 2 And KOH in a mass ratio of 0.5 to 0.6: 1; collecting the reaction product, washing and drying to obtain the pre-embedded K + delta-MnO of 2 。
6. The aqueous zinc ion battery according to claim 5, wherein the temperature of the positive electrode material hydrothermal reaction step is 150 ℃ and 170 ℃, and the reaction time is 60-80 h; the temperature of the drying step is 70-100 ℃, and the heating treatment is carried out for 1.5-3 h.
7. An aqueous zinc-ion battery according to claim 6, further preferably, the temperature of the positive electrode material hydrothermal reaction step is 160 ℃, the reaction time is 72 hours; the temperature of the drying step is 70 ℃, and the heating treatment is carried out for 2 h.
8. An aqueous zinc-ion battery according to claim 4, prepared by the following steps: mixing the positive electrode material, acetylene black and polyvinylidene fluoride according to a certain mass ratio, putting the mixture into an agate mortar, dripping N-methyl-2-pyrrolidone (NMP), grinding and mixing to prepare positive electrode slurry, coating the positive electrode slurry on a stainless steel mesh current collector, drying in an oven, and assembling the positive electrode current collector, a glass fiber diaphragm, a zinc foil negative electrode and an electrolyte to obtain the battery.
9. The aqueous zinc-ion battery according to claim 8, wherein the mass ratio of the positive electrode material, the acetylene black, and the polyvinylidene fluoride is 6-8: 1-3: 0.5-1.5, and the loading capacity of the positive electrode slurry is 1.8-2.2mg cm -2 The oven conditions are preferably: drying at 70-100 deg.C for 6-10h in air environment.
10. An aqueous zinc-ion battery according to claim 8, wherein the assembled battery is preferably a coin cell battery, more preferably a CR2032 coin cell battery.
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