CN114552030A - Low-cost environment-friendly aqueous zinc ion battery positive electrode material and preparation method thereof - Google Patents

Low-cost environment-friendly aqueous zinc ion battery positive electrode material and preparation method thereof Download PDF

Info

Publication number
CN114552030A
CN114552030A CN202210166839.7A CN202210166839A CN114552030A CN 114552030 A CN114552030 A CN 114552030A CN 202210166839 A CN202210166839 A CN 202210166839A CN 114552030 A CN114552030 A CN 114552030A
Authority
CN
China
Prior art keywords
mno
ion battery
low
cost
delta
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210166839.7A
Other languages
Chinese (zh)
Inventor
吕玮
武英
孟静雯
李一鸣
杨维结
田永兰
沈尧
吕雪峰
段聪文
马晓磊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
North China Electric Power University
Original Assignee
North China Electric Power University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by North China Electric Power University filed Critical North China Electric Power University
Priority to CN202210166839.7A priority Critical patent/CN114552030A/en
Publication of CN114552030A publication Critical patent/CN114552030A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention belongs to the technical field of water-based zinc ion battery materials, particularly relates to a low-cost environment-friendly water-based zinc ion battery positive electrode material, and further discloses a preparation method thereof. The preparation method of the low-cost environment-friendly water-based zinc ion battery cathode material adopts cheap, safe and environment-friendly gamma-MnO2Uses a simple hydrothermal method to prepare K as a raw material+Pre-embedded delta-MnO2Then adopting low-temperature argon annealing process to further produce oxygen vacancy in the material interior so as to synthesize the pre-embedded K+Oxygen vacancy-blended layered positive electrode material Birnessite type delta-MnO2Overcomes the defect that the prior art is based on KMnO4The synthesis process has the defects of high cost, complex process and high toxicity, has the advantages of low process cost, environmental friendliness, safety, no toxicity and excellent performance, and is suitable for large-scale production and amplification.

Description

Low-cost environment-friendly aqueous zinc ion battery positive electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of water-based zinc ion battery materials, particularly relates to a low-cost environment-friendly water-based zinc ion battery positive electrode material, and further discloses a preparation method thereof.
Background
With the continuous development of economy and the continuous improvement of science and technology, the demand of energy sources is gradually increased. However, the development and utilization of traditional fossil energy sources such as coal, oil, natural gas and the like have three outstanding problems: resource exhaustion, climate warming and environmental pollution. The development of renewable energy sources such as solar energy, wind energy, tidal energy and the like is a necessary trend for solving the outstanding problems of non-renewable energy sources and ensuring the sustainable development of human beings. In the current energy storage devices, lithium ion batteries are not suitable for the development of large-scale energy storage due to rising cost and outstanding safety problems. Therefore, development of a new water-based battery is of great practical significance.
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, wherein the most core factor influencing the electrochemical performance of the water system zinc ion battery is the positive electrode material, and how to obtain the positive electrode material with better performance is a difficult problem which is overcome by the great efforts of scientific researchers. To solve this problem, the main direction of research and development of aqueous zinc ion batteries should be to find new cathode materials with high capacity and wide potential window.
MnO2The nano material presents a plurality of special physicochemical properties due to the structural particularity, so that the nano material has wide prospect in the application of the fields of ion sieves, molecular sieves, catalytic materials, anode materials of lithium ion secondary batteries, novel magnetic materials and the like. Currently, MnO for positive electrode of aqueous zinc ion battery2The preparation technology mainly focuses on preparing MnO of a 1-dimensional tunnel structure2Wherein alpha-MnO2(size about 0.46nm) has been widely studied in favor of scholars because of its excellent cycling stability and multiplying power, however, it uses a raw material basically in KMnO4Mainly, and KMnO4Belongs to toxic and harmful controlled medicines and has high price, resulting in alpha-MnO2The synthesis process of the material has the problems of high production cost and non-ideal environmental friendliness.
Birnessite type delta-MnO2As a material with a layered structure, the interlayer spacing is about 0.7nm, in contrast to alpha-MnO2Theoretically, it is more suitable for the storage and release of zinc ions, however, delta-MnO2The layered structure is easily damaged in the charge and discharge process, and is not beneficial to the diffusion of ions in a material matrix, so that the cycle stability and the rate capability are poor. At present, with respect to delta-MnO2The research is still few, and the delta-MnO is prepared by adopting cheaper, safer and environment-friendly raw materials2The reports are more rare. For example, Xun et al use KMnO4Preparing alpha-MnO as raw material2The material is 0.2A g-1The discharge capacity at that time was 210mAh g-1、1A g-1Capacity of 50 cycles of the lower cycle has substantially no attenuation; alfaruqi et al used KMnO4And sulfuric acid as raw materials, and synthesizing alpha-MnO based on a hydrothermal method283mA g of the material-1The discharge capacity is 233mAh g-1The life of 50 cycles is 63%, the coulombic efficiency is close to 100%, 1333 and 1666mA g-1Lower capacities of 43.33 and 31.48mAh g, respectively-1(ii) a Lee et al used KMnO4The alpha-MnO is synthesized by a hydrothermal method210.5mA g of the material-1Lower capacity of 205mAh g-1The service life of 30 cycles is 66%; pan et al used KMnO4、H2SO4、MnSO4·H2O is used as a raw material, and alpha-MnO is synthesized based on a hydrothermal method261.6mA g of the material-1Lower capacity of 255mAh g-1The life of 400 cycles was 17.6%, at 616, 1540 and 3080mA g-1Lower capacities of 207, 161 and 113mAh g, respectively-1(ii) a Alfaruqi et al used KMnO4And Mn (CH)3COOH)2Preparing alpha-MnO for raw material216mA g of the material-1Lower capacity 323mAh g-1At 1666mA g-1Lower capacity of 47.16mAh g-1(ii) a Han et al used KMnO4And MnSO4·H2O preparation of delta-MnO2The discharge capacity of the material is 12.3mA/g and is 120mAh g-1And the service life of 125 cycles is 48 percent near the voltage platform of 1.25V. Thus, the conventional synthesis of alpha-MnO2Or delta-MnO2Are based on KMnO4Is a raw material, and the environmental protection and economic benefits can not be ensured. Therefore, the development of a gamma-MnO based on inexpensive and nontoxic materials has been made2Preparing anode material delta-MnO of water system zinc ion battery by using raw material2The process has positive significance.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a preparation method of a low-cost environment-friendly water-system zinc ion battery positive electrode material, and the method is based on cheap and nontoxic gamma-MnO2Is a raw material, and has the advantages of low process cost, environmental friendliness, safety, no toxicity or harm and excellent performance;
the second technical problem to be solved by the present invention is to provide the positive electrode material for the aqueous zinc-ion battery prepared by the above method.
In order to solve the technical problems, the preparation method of the low-cost environment-friendly water system zinc ion battery anode material comprises the following steps:
(1) taking gamma-MnO2Mixing with KOH solution, carrying out hydrothermal reaction under heat preservation, collecting reaction products, washing and drying to obtain pre-embedded K+delta-MnO of2Marked as KMO for standby;
(2) heating the obtained KMO in protective atmosphere to carry out low-temperature annealing treatment to obtain the product containing the pre-embedded K+And delta-MnO of oxygen vacancy2And marking as KMO-V to obtain the product.
Specifically, in the step (1), the γ -MnO2And KOH in a mass ratio of 0.5 to 0.6: 1.
specifically, in the step (1), the temperature of the hydrothermal reaction step is 150-170 ℃, the reaction time is 60-80h, and preferably 160 ℃ for 72 h.
Specifically, in the step (1), the drying step is carried out by heating at 70-100 ℃ for 1.5-3h, preferably at 70 ℃ for 2 h.
Specifically, in the step (2), the temperature of the low-temperature annealing treatment step is 250-350 ℃, and preferably 300 ℃ for annealing.
Specifically, in the step (2), the heating rate of the heating step is 3-5 ℃ for min-1min-1。
Specifically, in the step (2), the time of the heating treatment step is 1.5 to 3 hours, and the treatment time is preferably 2 hours.
Specifically, in the step (2), the protective atmosphere includes argon.
The invention also discloses a water system zinc ion battery anode material prepared by the method, and the material contains pre-embedded K+Layered Birnessite type delta-MnO with oxygen vacancy2A material.
The invention also discloses application of the water-system zinc ion battery positive electrode material in preparation of a water-system zinc ion battery positive electrode or a water-system zinc ion battery.
The invention also discloses a water-system zinc ion battery positive electrode or a water-system zinc ion battery prepared from the water-system zinc ion battery positive electrode material.
The preparation method of the low-cost environment-friendly water-based zinc ion battery cathode material adopts cheap, safe and environment-friendly gamma-MnO2Uses a simple hydrothermal method to prepare K as a raw material+Pre-embedded delta-MnO2Then adopting low-temperature argon annealing process to further produce oxygen vacancy in the material interior so as to synthesize the pre-embedded K+Oxygen vacancy-blended layered positive electrode material Birnessite type delta-MnO2Overcomes the defect that the prior art is based on KMnO4The synthesis process has the defects of high cost, complex process and high toxicity, has the advantages of low process cost, environmental friendliness, safety, no toxicity and excellent performance, and is suitable for large-scale production and amplification.
The anode material Birnessite type delta-MnO of the water system zinc ion battery2By mixing K+Pre-embedded delta-MnO2The 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; meanwhile, the reaction activity of the material is improved while the electronic structure of the material is changed by introducing oxygen vacancies, so that the whole performance of the battery system is improved.
Drawings
In order that the present disclosure may be more readily and clearly understood, the following detailed description of the present disclosure is provided in connection with specific embodiments thereof and the accompanying drawings, in which,
FIG. 1 shows KMO-V, KMO, delta-MnO prepared in example 1 and comparative examples 1-32-V、δ-MnO2An XRD pattern of (a);
FIG. 2 shows KMO-V, KMO, delta-MnO prepared in example 1 and comparative examples 1 to 32-V、δ-MnO2(ii) a Raman spectrum of (a);
FIG. 3 shows KMO-V, KMO, delta-MnO prepared in example 1 and comparative examples 1 to 32-V、δ-MnO2Electron paramagnetic resonance spectrum of (a);
FIG. 4 shows KMO-V at 100mA g in example 1-1Discharge capacity-voltage curve graph of 10 th circle under current density;
FIG. 5 is a graph showing the rate performance of KMO-V in example 1;
FIG. 6 is a graph showing the discharge capacity decay curve of KMO-V in example 1;
FIG. 7 shows KMO in 100mA g in comparative example 1-1Discharge capacity-voltage curve graph of 10 th circle under current density;
FIG. 8 is a graph of the KMO rate performance in comparative example 1;
FIG. 9 is a graph showing the discharge capacity decay curve of KMO in comparative example 1;
FIG. 10 shows delta-MnO in comparative example 22V at 100mA g-1Discharge capacity-voltage curve graph of 10 th circle under current density;
FIG. 11 shows delta-MnO in comparative example 22-a graph of rate performance of V;
FIG. 12 shows delta-MnO in comparative example 22-discharge capacity decay curve of V;
FIG. 13 shows delta-MnO in comparative example 32At 100mA g-1The discharge capacity-voltage curve diagram of the 10 th circle under the current density;
FIG. 14 shows delta-MnO in comparative example 32The rate performance curve of (1);
FIG. 15 shows delta-MnO in comparative example 32Discharge capacity decay graph of (a).
Detailed Description
Example 1
The preparation method of the low-cost environment-friendly water-based zinc ion battery positive electrode material KMO-V comprises the following steps:
(1) 7.5g of commercial gamma-MnO was taken2Mixing with 60ml of KOH solution with the concentration of 4mol/L, putting the mixture into a hydrothermal reaction kettle with the volume of L00ml, carrying out heat preservation hydrothermal reaction for 72 hours at 160 ℃, collecting a product, cooling the product to room temperature, washing the obtained product with deionized water for 3 times, putting the product into an oven, heating the product for 2 hours at 70 ℃ to obtain the pre-embedded K+delta-MnO of2Denoted as KMO;
(2) the KMO obtained was heated at 5 deg.C for min in an argon furnace-1At a rate of temperature riseAnnealing at 300 deg.C for 2h, collecting the product, cooling to room temperature to obtain the product containing pre-embedded K+And delta-MnO of oxygen vacancy2And marking as KMO-V to obtain the product.
Example 2
The preparation method of the low-cost environment-friendly water-based zinc ion battery positive electrode material KMO-V comprises the following steps:
(1) according to the weight ratio of 0.5: 1 mass ratio of commercial γ -MnO2Preparing a solution with KOH with proper concentration, and adding the gamma-MnO2Mixing with KOH solution, placing into a hydrothermal reaction kettle with a volume of l00ml, performing thermal insulation hydrothermal reaction at 150 ℃ for 80h, collecting the product, cooling to room temperature, washing the obtained product with deionized water for 3 times, placing into an oven at 100 ℃ and heating for 1.5h to obtain pre-embedded K+delta-MnO of2Denoted as KMO;
(2) the KMO obtained was heated at 3 deg.C for min in an argon furnace-1Heating to 250 ℃ at a certain speed, carrying out low-temperature annealing treatment for 3h, collecting the product, and cooling to room temperature to obtain the product containing the pre-embedded K+And oxygen vacancy delta-MnO2And marking as KMO-V to obtain the product.
Example 3
The preparation method of the low-cost environment-friendly water-based zinc ion battery positive electrode material KMO-V comprises the following steps:
(1) according to the weight ratio of 0.6: 1 mass ratio of commercial γ -MnO2And KOH to a solution of appropriate concentration, and adding said gamma-MnO2Mixing with KOH solution, placing into a hydrothermal reaction kettle with a volume of l00ml, carrying out thermal insulation hydrothermal reaction at 170 ℃ for 60h, collecting the product, cooling to room temperature, washing the obtained product with deionized water for 3 times, placing into an oven at 70 ℃ and heating for 3h to obtain pre-embedded K+delta-MnO of2Denoted as KMO;
(2) the KMO obtained was heated at 4 deg.C for min in an argon furnace-1Heating to 350 ℃ at a certain speed, carrying out low-temperature annealing treatment for 1.5h, collecting the product, and cooling to room temperature to obtain the product containing the pre-embedded K+And delta-MnO of oxygen vacancy2And marking as KMO-V to obtain the product.
Comparative example 1
7.5g of commercial gamma-MnO was taken2Mixing with 60ml of KOH solution with the concentration of 4mol/L, putting the mixture into a hydrothermal reaction kettle with the volume of L00ml, carrying out heat preservation hydrothermal reaction for 72 hours at 160 ℃, collecting a product, cooling the product to room temperature, washing the obtained product with deionized water for 3 times, putting the product into an oven, heating the product for 2 hours at 70 ℃ to obtain the pre-embedded K+delta-MnO of2Denoted as KMO.
Comparative example 2
7.5g of commercial gamma-MnO was taken2Mixing with 60ml of KOH solution with the concentration of 4mol/L, putting the mixture into a hydrothermal reaction kettle with the volume of L00ml, carrying out heat preservation hydrothermal reaction at 160 ℃ for 72 hours, collecting a product, cooling the product to room temperature, washing the obtained product with deionized water for 3 times, putting the product into an oven at 70 ℃ and heating the product for 2 hours to obtain the pre-embedded K+delta-MnO of2Denoted as KMO;
the KMO obtained was heated at 5 deg.C for min in an argon furnace-1Heating to 300 ℃ at a certain speed, carrying out low-temperature annealing treatment for 2 hours, collecting the product, and cooling to room temperature to obtain the product containing the pre-embedded K+And delta-MnO of oxygen vacancy2And is marked as KMO-V;
the obtained KMO-V was immersed in 0.8mol L of-1HNO3Lasting for 24h, washing the obtained product with deionized water for 3 times, putting the product into an oven, heating the product for 2h at 70 ℃, and cooling the product to room temperature to obtain the product containing no K+And delta-MnO containing oxygen vacancies2Is denoted as delta-MnO2-V。
Comparative example 3
7.5g of commercial gamma-MnO was taken2Mixing with 60ml of KOH solution with the concentration of 4mol/L, putting the mixture into a hydrothermal reaction kettle with the volume of L00ml, carrying out heat preservation hydrothermal reaction for 72 hours at 160 ℃, collecting a product, cooling the product to room temperature, washing the obtained product with deionized water for 3 times, putting the product into an oven, heating the product for 2 hours at 70 ℃ to obtain the pre-embedded K+delta-MnO of2Denoted as KMO;
the obtained KMO was immersed in 0.8mol L of-1HNO3Lasting for 24h, washing the obtained product with deionized water for 3 times, putting the product into an oven, heating the product for 2h at 70 ℃, and cooling the product to room temperature to obtain the product without K+And does not contain delta-MnO containing O vacancies2Is denoted as delta-MnO2。
Examples of the experiments
First, spatial structure detection
FIGS. 1 to 3 show KMO-V, KMO and delta-MnO prepared in example 1 and comparative examples 1 to 3, respectively2-V、δ-MnO2The XRD spectrum, Raman spectrum and electron paramagnetic resonance spectrum results.
As can be seen from the results shown in FIGS. 1 to 3, the KMO-V prepared in example 1 of the present invention is birnessite type delta-MnO2(JCPDS 42-1317) and the KMO-V contains a certain amount of oxygen vacancies.
As can be seen from the results of FIGS. 1 to 3, the KMO prepared in comparative example 1 of the present invention is birnessite type delta-MnO2(JCPDS 42-1317), the KMO contains substantially no or only a small amount of oxygen vacancies.
As can be seen from the results of FIGS. 1 to 3, the delta-MnO prepared in comparative example 2 of the present invention2V is birnessite type delta-MnO2(JCPDS 42-1317), the delta-MnO2V contains a certain amount of oxygen vacancies.
As can be seen from the results of FIGS. 1 to 3, the delta-MnO prepared in comparative example 3 of the present invention2Is birnessite type delta-MnO2(JCPDS 42-1317), the delta-MnO2Substantially free or only containing a small amount of oxygen vacancies.
Second, testing electrical properties
Respectively taking the positive electrode materials (KMO-V, KMO, delta-MnO)2-V、δ-MnO2) Acetylene black, polyvinylidene fluoride (PVDF), in a mass ratio of 7: 2: 1 (0.07 g: 0.02 g: 0.01g) is put into an agate mortar, 0.3-0.5 ml of n-methyl-2-pyrrolidone is dripped into the mixture, the mixture is ground and mixed to prepare anode slurry, a soft blade is coated on a stainless steel mesh current collector with the diameter of 14mm, the mixture is dried for 6-10h at 70-100 ℃ in an oven under the air environment, and the loading capacity of the anode slurry is 1.8-2.2mg cm-2Positive electrode current collector, glass fiber diaphragm, zinc foil negative electrode, 0.2-0.25ml electrolyte (wherein KMO-V, KMO uses 2mol L electrolyte- 1ZnSO4、0.1mol L-1MnSO4、0.1mol L-1K2SO4Mixed liquor, delta-MnO2-V、δ-MnO2The electrolyte used was 2mol L- 1ZnSO4、0.1mol L-1MnSO4Mixed solution), and charging into 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 mass of the positive active material.
1. Discharge capacity test
Respectively for positive electrode materials (KMO-V, KMO, delta-MnO)2-V、δ-MnO2) The formed button cell is subjected to discharge capacity test, and the specific steps comprise:
step 1: 100mA g-1Charging to the potential of 1.8V;
step 2: 100mA g-1Discharging 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. 4, 7, 10 and 13 are based on KMO-V, KMO and delta-MnO, respectively2-V、δ-MnO2The formed button cell is 100mA g-1Discharge capacity-voltage plot at 10 th cycle at current density.
As can be seen from the results of FIG. 4, the initial KMO-V discharge voltage was 1.8V, and the discharge capacity was 288.8mAh g-1Coulombic efficiency 99.88%, energy density 389.88Wh Kg-1。
As can be seen from the results of FIG. 7, the initial KMO discharge voltage was 1.75V, and the discharge capacity was 210.7mAh g-1Coulombic efficiency 95.36%, energy density 284.45Wh Kg-1。
As can be seen from the results of FIG. 10, delta-MnO2Initial discharge voltage of-V1.72V, discharge capacity of 137.5mAh g-1Coulombic efficiency 92.61%, energy density 185.63Wh Kg-1。
As can be seen from the results of FIG. 13, delta-MnO2Initial discharge voltage 1.7V, discharge capacity 103.3mAh g-1Coulombic efficiency 90.15%, energy density 139.46Wh Kg-1。
2. High rate performance test
Respectively for positive electrode materials (KMO-V, KMO, delta-MnO)2-V、δ-MnO2) The formed button cell is multipliedThe rate performance test comprises the following specific steps:
step 1: 100mA g-1Charging to a potential of 1.8V;
step 2: 100mA g-1Discharging to 0.8V;
and step 3: repeating the step 1-2 until the charging and discharging times of the battery are 10;
and 4, step 4: 200mA g-1Charging to a potential of 1.8V;
and 5: 200mA g-1Discharging to 0.8V;
step 6: repeating the steps 4-5 until the charging and discharging times of the battery are 10;
and 7: 400mA g-1Charging to a potential of 1.8V;
and 8: 400mA g-1Discharging 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-1Charging to a potential of 1.8V;
step 11: 600mA g-1Discharging 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-1Charging to a potential of 1.8V;
step 14: 800mA g-1Discharging 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-1Charging to a potential of 1.8V;
and step 17: 1A g-1Discharging 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: 100mA g-1Charging to a potential of 1.8V;
step 20: 100mA g-1Discharging to 0.8V;
step 21: and repeating the steps 19-20 until the number of charging and discharging times of the battery is 10.
FIGS. 5, 8, 11 and 14 are based on KMO-V, KMO, delta-Mn, respectivelyO2-V、δ-MnO2And (4) forming a multiplying power performance curve diagram of the button cell.
As can be seen from the results in FIG. 5, KMO-V was measured at 100mA g-1N at current densityaIs 10, 200mA g-1Discharge capacity 251.6-275.6mAh g-1，400mA g-1Discharge capacity of 216.7-238.7mAh g-1，600mA g-1Discharge capacity of 187.5-204.5mAh g-1，800mA g-1The discharge capacity is 146.5-174.2mAh g-1，1A g-1Discharge capacity of 82.4-131.4mAh g-1. After charge-discharge cycling, 100mA g-1The discharge capacity can still be recovered to be close to 288.8mAh g-1。
As can be seen from the results in FIG. 8, KMO was measured at 100mA g-1N at current densityaIs 10, 200mA g-1Discharge capacity 185.6-201.8mAh g-1，400mA g-1Discharge capacity of 151.7-173.2mAh g-1，600mA g-1Discharge capacity of 127.5-143.5mAh g-1，800mA g-1Discharge capacity of 81.1-118.3mAh g-1，1A g-1Discharge capacity of 46.4-70.4mAh g-1. After charge-discharge cycling, 100mA g-1The discharge capacity can still be recovered to be close to 210.7mAh g-1。
As can be seen from the results in FIG. 11, the delta-MnO2V at 100mA g-1N at current densityaIs 10, 200mA g-1Discharge capacity of 118.6-132.6mAh g-1，400mA g-1Discharge capacity of 96.7-110.7mAh g-1，600mA g-1Discharge capacity of 76.5-92.5mAh g-1，800mA g-1Discharge capacity of 44.1-66.7mAh g-1，1A g-1Discharge capacity of 18.4-37.9mAh g-1. After charge-discharge cycling, 100mA g-1The discharge capacity can still be recovered to be close to 137.5mAh g-1。
As can be seen from the results in FIG. 14, delta-MnO2At 100mA g-1N at current densityaIs 10, 200mA g-1Discharge capacity of 86.6-97.4mAh g-1，400mA g-1Discharge capacity of 58.3-77.7mAh g-1，600mA g-1Discharge capacity of 35.5-52.4mAh g-1，800mA g-1Discharge capacity of 14.1-29.4mAh g-1，1A g-1Discharge capacity of 0.02-9.4mAh g-1. After charge-discharge cycling, 100mA g-1The discharge capacity can still be recovered to be close to 103.3mAh g-1。
3. Cycle performance test
Respectively for positive electrode materials (KMO-V, KMO, delta-MnO)2-V、δ-MnO2) Performing cycle performance tests on the formed button battery, wherein the cycle performance tests comprise 500 times of cycle tests and 1500 times of cycle tests; wherein:
the test is circulated for 500 times, and the specific steps comprise:
step 1: 600mA g-1Charging to a potential of 1.8V;
step 2: 600mA g-1Discharging to 0.8V;
and step 3: repeating the steps 1-2 until the charge-discharge cycle reaches 500 times.
Capacity retention rate (S) for 500 charge-discharge cycle stability500) To characterize:
S500＝C500/Cmax
in the formula, C500Represents 600mA g-1Discharge capacity at the next 500 th cycle, CmaxRepresents 600mA g-1Lower maximum discharge capacity;
and (3) circulating 1500 times of tests, and specifically comprising the following steps:
step 1: 1A g-1Charging to a potential of 1.8V;
step 2: 1A g-1Discharging to 0.8V;
and step 3: repeating the steps 1-2 until the charge-discharge cycle reaches 1500 times.
Capacity retention ratio (S) for 1500 times of charge-discharge cycle stability1500) To characterize:
S1500＝C1500/Cmax
in the formula, C1500Representation 1A g-1Discharge capacity at the next 1500 th cycle, CmaxRepresentation 1A g-1The lower maximum discharge capacity.
FIGS. 6, 9, 12 and 15 are based on KMO-V, KMO and delta-MnO, respectively2-V、δ-MnO2And (4) a discharge capacity decay curve chart of the formed button cell.
As can be seen from the results in FIG. 6, KMO-V was operated at 600mA g-1Lower S50089.4% at 1A g-1Lower S1500The content was 91.9%.
As can be seen from the results in FIG. 9, KMO was performed at 600mA g-1Lower S500At 31.6% at 1A g-1Lower S1500The content was 39.6%.
As can be seen from the results in FIG. 12, delta-MnO2V at 600mA g-1Lower S500At 24.7%, at 1A g-1Lower S1500The content was 28.3%.
As can be seen from the results in FIG. 15, the delta-MnO 2 was at 600mA g-1Lower S500At 12.2% at 1A g-1Lower S1500The content was 14.4%.
In conclusion, the anode material Birnessite type delta-MnO of the water-based zinc ion battery2By mixing K+Pre-embedded delta-MnO2The layered structure and the introduction of oxygen vacancies improve the reaction activity of the material while changing the electronic structure of the material, so that the whole performance of the battery system is improved.
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. A preparation method of a low-cost environment-friendly water system zinc ion battery anode material is characterized by comprising the following steps:
(1) taking gamma-MnO2Mixing with KOH solution, keeping the temperature for hydrothermal reaction, collecting reaction products, washing anddrying to obtain pre-embedded K+delta-MnO of2Marked as KMO for standby;
(2) heating the obtained KMO in protective atmosphere to carry out low-temperature annealing treatment to obtain the product containing the pre-embedded K+And delta-MnO of oxygen vacancy2And marking as KMO-V to obtain the product.
2. The method for preparing a positive electrode material for a low-cost and environmentally friendly aqueous zinc-ion battery according to claim 1, wherein the γ -MnO is added in the step (1)2And KOH in a mass ratio of 0.5 to 0.6: 1.
3. the preparation method of the low-cost environment-friendly water-based zinc ion battery cathode material as claimed in claim 1 or 2, wherein in the step (1), the temperature of the hydrothermal reaction step is 150-170 ℃, and the reaction time is 60-80 h.
4. The preparation method of the cathode material of the low-cost and environment-friendly water-based zinc ion battery as claimed in any one of claims 1 to 3, wherein in the step (1), the temperature of the drying step is 70-100 ℃ for heat treatment for 1.5-3 h.
5. The method for preparing the cathode material of the low-cost and environment-friendly water-based zinc-ion battery as claimed in any one of claims 1 to 4, wherein the temperature of the low-temperature annealing treatment step in the step (2) is 250-350 ℃.
6. The method for preparing the cathode material of the low-cost and environment-friendly water-based zinc-ion battery as claimed in any one of claims 1 to 5, wherein in the step (2), the temperature rise rate of the temperature rise step is 3 to 5 ℃ for min-1。
7. The method for preparing the cathode material of the low-cost and environment-friendly water-based zinc-ion battery as claimed in any one of claims 1 to 6, wherein the time of the low-temperature annealing treatment step in the step (2) is 1.5 to 3 hours.
8. The method for preparing a positive electrode material for a low-cost and environmentally friendly aqueous zinc-ion battery according to any one of claims 1 to 7, wherein the protective atmosphere in the step (2) comprises argon.
9. The water-based zinc ion battery positive electrode material prepared by the method of any one of claims 1 to 8, wherein the material contains pre-embedded K+Oxygen vacancy-blended layered Birnessite type delta-MnO2A material.
10. Use of the aqueous zinc-ion battery positive electrode material according to claim 9 for producing an aqueous zinc-ion battery positive electrode or an aqueous zinc-ion battery.
CN202210166839.7A 2022-02-23 2022-02-23 Low-cost environment-friendly aqueous zinc ion battery positive electrode material and preparation method thereof Pending CN114552030A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210166839.7A CN114552030A (en) 2022-02-23 2022-02-23 Low-cost environment-friendly aqueous zinc ion battery positive electrode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210166839.7A CN114552030A (en) 2022-02-23 2022-02-23 Low-cost environment-friendly aqueous zinc ion battery positive electrode material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN114552030A true CN114552030A (en) 2022-05-27

Family

ID=81676622

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210166839.7A Pending CN114552030A (en) 2022-02-23 2022-02-23 Low-cost environment-friendly aqueous zinc ion battery positive electrode material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114552030A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115117468A (en) * 2022-07-13 2022-09-27 华北电力大学 Birnessite type delta-MnO for improving zinc electricity of water system 2 Electrolyte with positive polarity and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000079622A1 (en) * 1999-06-23 2000-12-28 Eveready Battery Company, Inc. Performance enhancing additives for electrochemical cells
CN106972168A (en) * 2017-05-17 2017-07-21 哈尔滨工业大学 A kind of preparation method and application of the manganese dioxide containing Lacking oxygen/sulphur composite
CN112886004A (en) * 2021-01-11 2021-06-01 北京科技大学 Cathode material of water-based zinc ion battery and matched electrolyte
CN113707868A (en) * 2021-08-31 2021-11-26 中国地质大学（北京） Ternary composite electrode material, preparation method thereof and zinc ion battery
CN113772735A (en) * 2021-06-30 2021-12-10 浙江长兴绿色电池科技有限公司 Doped manganese dioxide and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000079622A1 (en) * 1999-06-23 2000-12-28 Eveready Battery Company, Inc. Performance enhancing additives for electrochemical cells
CN106972168A (en) * 2017-05-17 2017-07-21 哈尔滨工业大学 A kind of preparation method and application of the manganese dioxide containing Lacking oxygen/sulphur composite
CN112886004A (en) * 2021-01-11 2021-06-01 北京科技大学 Cathode material of water-based zinc ion battery and matched electrolyte
CN113772735A (en) * 2021-06-30 2021-12-10 浙江长兴绿色电池科技有限公司 Doped manganese dioxide and preparation method thereof
CN113707868A (en) * 2021-08-31 2021-11-26 中国地质大学（北京） Ternary composite electrode material, preparation method thereof and zinc ion battery

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DENGHU WANG等: "Engineering the interplanar spacing of K-birnessite for ultra-long cycle Zn-ion battery through "hydrothermal potassium insertion" strategy", 《CHEMICAL ENGINEERING JOURNAL》, vol. 435, pages 134754 *
KUN HAN等: "High-performance aqueous Zn–MnO2 batteries enabled by the coupling engineering of K+ preintercalation and oxygen defects", 《JOURNAL OF MATERIALS CHEMISTRY A》, vol. 9, pages 15637 - 15647 *
Q. FENG等: "Hydrothermal synthesis and metal ion adsorptive property of birnessitetype potassium manganese oxide", 《JOURNAL OF MATERIALS SCIENCE LETTERS》, vol. 15, pages 963 - 965 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115117468A (en) * 2022-07-13 2022-09-27 华北电力大学 Birnessite type delta-MnO for improving zinc electricity of water system 2 Electrolyte with positive polarity and preparation method thereof
CN115117468B (en) * 2022-07-13 2024-02-13 华北电力大学 Lifting water system zinc-electricity Birnesite delta-MnO 2 Electrolyte with positive electrode performance and preparation method thereof

Similar Documents

Publication Publication Date Title
CN112886004B (en) Cathode material of water-based zinc ion battery and matched electrolyte
CN105470455A (en) Modified lithium ion battery positive electrode material and preparation method therefor
CN104795555B (en) A kind of aqueous solution sodium-ion battery and its positive electrode, preparation method and purposes
CN108598394B (en) Carbon-coated titanium manganese phosphate sodium microspheres and preparation method and application thereof
CN108172815B (en) Microspherical zinc vanadate, and preparation method and application thereof
CN111092220A (en) M-element bulk phase doped modified manganese-based positive electrode material of tunnel-type sodium-ion battery and preparation method thereof
CN110176601A (en) A kind of carbon coating oxidation Asia silicium cathode material and its preparation method and application
CN102623707A (en) Cobalt-doped carbon-coated ferric fluoride anode material and preparation method thereof
CN109809485A (en) A kind of height ratio capacity hydration vanadic acid magnesium and the preparation method and application thereof
CN111082003A (en) Vanadate hydrate electrode material and preparation method and application thereof
CN113422048B (en) Preparation method and application of anode material of water-based zinc ion battery
CN108448071A (en) A kind of method of fabricated in situ porous nano cobaltosic oxide/carbon negative pole material
CN109037649A (en) It is a kind of to be mixed with modified nickel cobalt lithium aluminate cathode material and preparation method thereof
CN104157858A (en) Hierarchical porous ferroferric oxide / graphene nano wire and preparation method and application thereof
CN104124429A (en) Lithium vanadium oxide/carbon nano tube composite material with hollow structure and preparation method and application of lithium vanadium oxide/carbon nano tube composite material with hollow structure
CN115057485A (en) Non-metal boron-doped layered oxide sodium ion battery positive electrode material and preparation method and application thereof
CN110931779A (en) High-capacity long-life aqueous zinc ion battery positive electrode material and preparation method thereof
CN106450284A (en) Method for preparing hollow-microsphere lithium manganate positive electrode material with higher electrochemical properties
CN114590838B (en) Amorphous metal sulfide coated modified binary manganese-based sodium electro-precursor and preparation method thereof
CN106410154A (en) Preparation method of carbon-coated iron borate material and application of carbon-coated iron borate material in sodium ion batteries
CN112054174A (en) Potassium ion battery negative electrode material and preparation method and application thereof
CN106784803A (en) A kind of cobalt acid nickel nanocube material and its preparation method and application
CN104241628A (en) Method for preparing titanium-dioxide-modified ferric oxide microspheres as well as produced product and use of titanium-dioxide-modified ferric oxide microspheres
CN114552030A (en) Low-cost environment-friendly aqueous zinc ion battery positive electrode material and preparation method thereof
CN106920952B (en) A kind of preparation method of modified nickel lithium manganate cathode material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination