CN115331978A - Preparation method and application of positive and negative electrode matching material of lithium ion hybrid capacitor - Google Patents

Preparation method and application of positive and negative electrode matching material of lithium ion hybrid capacitor Download PDF

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CN115331978A
CN115331978A CN202211069366.5A CN202211069366A CN115331978A CN 115331978 A CN115331978 A CN 115331978A CN 202211069366 A CN202211069366 A CN 202211069366A CN 115331978 A CN115331978 A CN 115331978A
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precursor
mno
lithium ion
negative electrode
positive
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邓齐波
安翠华
胡宁
武帅
高玲肖
张静宇
焦朋港
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Hebei University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • 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
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention relates to a preparation method of a positive and negative electrode matching material of a lithium ion hybrid capacitor, which comprises the following steps: dissolving 0.2-0.8 g of manganese chloride tetrahydrate and 1.0-1.5 g of nitrosotriacetic acid in a solution of ultrapure water and isopropanol in a volume ratio of 1; repeatedly washing the obtained precursor with ultrapure water and ethanol, drying the washed precursor in an oven at 80 ℃ overnight to obtain a precursor, and dividing the precursor into two parts; calcining one part of the precursor for 1-3 h at 400-600 ℃ under the protective atmosphere, and cooling to room temperature after the calcination is finished to obtain a MnO @ C material; carbonizing the other part of precursor for 1-3 h at 700-900 ℃ under a protective atmosphere, cooling to room temperature after calcination, treating with 0.01-0.1M HF solution, and repeatedly washing with ultrapure water and ethanol to obtain the porous carbon material. The assembled lithium ion hybrid capacitor has high energy density, high power density and excellent stability.

Description

Preparation method and application of positive and negative electrode matching material of lithium ion hybrid capacitor
Technical Field
The invention belongs to the field of lithium ion hybrid capacitors, and particularly relates to a preparation method and application of a positive and negative electrode matching material of a lithium ion hybrid capacitor.
Background
Today, to meet the ever-increasing demands of portable electronics, battery-powered automobiles, smart or large-scale power grids, energy storage systems must be equipped with higher energy and power densities, as well as longer cycle life. The lithium-ion hybrid capacitor, as a novel energy storage device, inherits the advantages of an electrochemical super capacitor and a lithium-ion battery, and shows high energy density at ultrahigh power density without sacrificing durability performance. However, the electrochemical performance of lithium-ion hybrid capacitors is always limited by the diversity and mismatch of the positive and negative electrode materials.
Carbon-based materials and modified transition metal oxides have been successfully prepared and used as the positive and negative electrodes of lithium ion hybrid supercapacitors. Transition metal oxides have the advantages of high theoretical capacity, high reserves, rich valences and low cost but generally exhibit poor cycling stability and poor rate capability. The lower discharge capacity of the carbon-based material limits the energy density of the lithium ion hybrid capacitor.
In addition, the mismatch between the positive and negative electrode materials of the lithium ion hybrid capacitor poses problems with respect to energy density, rate capability, power density, and long cycle stability. In addition, in the preparation process, the electrode material is usually required to be prepared separately, so that the preparation period is long and the cost is difficult to control. Therefore, the development of the positive and negative electrode materials of the lithium ion hybrid capacitor which are easy to produce and matched with each other has great significance and value for the development and application of the high-performance lithium ion hybrid capacitor.
Literature (Ninglong, addesheng, lvzrre, congfuyu, huangzhenghong, porous carbon composite V) 2 O 3 Research on application of nano material to lithium ion capacitor [ J]A novel carbon material, 2021,36 (06): 1103-1108), discloses a V 2 O 3 @ C/commercial activated carbon assembled into a lithium ion hybrid capacitor. The composite material V of the hybrid capacitor 2 O 3 The preparation of the precursor of @ C needs 13h of stirring and 24h of freeze drying, the time consumption of the preparation process is long, the equipment requirement is high, and the large-scale production is not facilitated.
Disclosure of Invention
The invention provides a preparation method and application of a positive and negative electrode matching material of a lithium ion hybrid capacitor, aiming at the defects in the preparation of the positive and negative electrode materials of the lithium ion hybrid capacitor in the prior art. The preparation method is simple in process, and the prepared anode and cathode materials have excellent electrochemical properties.
The technical scheme for solving the technical problems is as follows: relates to a preparation method of a positive and negative electrode matching material of a lithium ion hybrid capacitor, which is characterized by comprising the following steps:
step 1: 0.2-0.8 g of manganese chloride tetrahydrate (MnCl) 2 ·4H 2 O) and 1.0 to 1.5g of nitrosotriacetic acid (SNA) are dissolved in a solution with the volume ratio of ultrapure water to isopropanol being 1;
and 2, step: transferring the homogeneous solution obtained in the step 1 into an autoclave, sealing and keeping at 150-200 ℃ for 4-8 h, cooling to 25 ℃ after heating, and collecting a precursor through vacuum filtration;
and 3, step 3: repeatedly washing the precursor obtained in the step 2 by using ultrapure water and ethanol, and drying the washed precursor in an oven at 80 ℃ overnight to obtain a precursor Mn-SNA complex, and dividing the precursor into two parts;
and 4, step 4: transferring one of the precursors obtained in the step 3 into a corundum boat, calcining the corundum boat in a tubular furnace at the temperature of 400-600 ℃ for 1-3 h under the protective atmosphere, and cooling to room temperature after the calcination is finished to obtain MnO @ C;
and 5: transferring the other part of the precursor obtained in the step 3 into a corundum boat, carbonizing the corundum boat in a tube furnace at the temperature of 700-900 ℃ for 1-3 h under protective atmosphere, and cooling to room temperature after calcination;
step 6: and (3) treating the powder obtained in the step (5) by using 0.01-0.1M HF, and then repeatedly washing the powder by using ultrapure water and ethanol to obtain the porous carbon material (PC) of the cathode material.
In step 1, 0.6g of manganese chloride tetrahydrate and 1.2g of nitrosotriacetic acid were added.
In the step 2, the temperature of the high-pressure kettle is 180 ℃, and the heat preservation time is 6 hours; in the step 4, the calcining temperature is 500 ℃, the heat preservation time is 2 hours, and the calcining is carried out under the Ar atmosphere; in the step 5, the calcining temperature is 800 ℃, the heat preservation time is 2 hours, and the protective atmosphere is N 2 Atmosphere; in step 6, the concentration of the HF solution was 0.05M.
The matching material in the application is the performance matching achieved by a capacitor device formed by a positive electrode material and a negative electrode material, and is not particularly limited to one electrode of the positive electrode material or the negative electrode material or a mixture of the positive electrode material and the negative electrode material. The main goal in designing hybrid energy storage devices is to develop a high power device that combines the high energy of a secondary battery and the high power of a super capacitor. The basic principle of matching is to select high capacitance materials to increase energy density and to select high rate battery materials to increase power density. Due to different energy storage mechanisms, the battery capacitor cannot achieve expected performance under high rate and low rate at the same time, and the method adjusts the types of raw materials and reaction conditions for preparing the positive electrode and the negative electrode according to application requirements to obtain the optimal performance.
Further, the invention relates to an application of the anode and cathode matching material of the lithium ion hybrid capacitor, wherein the MnO @ C material and the porous carbon material (PC) obtained by the preparation method are as follows: firstly, dispersing 10% of acetylene black, 80% of MnO @ C material and 10% of Polytetrafluoroethylene (PVDF) in an N-methylpyrrolidone (NMP) solution to generate uniform slurry, coating the slurry on a copper foil and drying in an oven to obtain single-electrode MnO @ C; acetylene black is added into a porous carbon material (PC), and finally the porous carbon material is coated on an aluminum foil to form a single electrode PC.
After 3000 cycles, the capacitance of a device MnO @ C// PC assembled by the matching material can still keep more than 80% of the initial value, and the capacitor has high energy density, high power density and excellent stability.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method provided by the invention adopts the same metal complex as a precursor, and can be simultaneously used for preparing subsequent anode and cathode materials (the anode material is porous carbon PC, the cathode material is MnO @ C, and the precursors are both metal complexes of Mn, wherein MnO @ C is prepared in step 4, and porous carbon PC is prepared in steps 5 and 6); the invention takes PC material as the anode of the capacitor, mnO @ C as the cathode of the capacitor; the two materials are respectively used for different side electrodes; the MnO and C are integrated into an MnO @ C core-shell structure, so that the MnO @ C has high capacity and good cycle stability as a negative electrode material, and the performance of a mixed capacitor device consisting of a positive electrode material and a negative electrode material is matched, so that the lithium ion mixed capacitor has excellent performance.
(2) In the preparation method, nitrosotriacetic acid (SNA) and manganese chloride tetrahydrate (MnCl) are selected 2 ·4H 2 O) is used as a raw material of a precursor, and metal salt/metal ions form stable complexation with a chelating agent in a specific system of ultrapure water and isopropanol, so that the structures between metal oxides and C in MnO @ C are similar as much as possible, and the volumes of the metal oxides and C in the dynamic change process are adaptive; the metal-organic complex precursor can be converted into carbon material and metal compound, and the structure between the derived carbon material and the metal oxide is similar, so that the calcination in step 4MnO can be formed after firing instead of forming other Mn oxides. The positive electrode material and the negative electrode material have similar structures and have synergistic effect, and the lithium ion hybrid capacitor assembled by the positive electrode material and the negative electrode material has high energy density, high power density and excellent stability, and has guiding significance for developing a novel positive electrode material and a novel negative electrode material of the lithium ion hybrid capacitor.
(3) The preparation method only comprises the steps of high-pressure kettle heating, calcining, washing, drying and the like, and is simple. The prepared device is assembled by the anode and cathode matching materials of the lithium ion hybrid capacitor, and the weight is 48W kg -1 Shows 89Wh kg at power density -1 And an energy density of 45Wh kg -1 At an energy density of 18kW kg of battery -1 The power density of (2).
(4) The preparation method of the anode and cathode matching material of the lithium ion hybrid capacitor mainly comprises the following steps: dissolving manganese chloride tetrahydrate and nitrosotriacetic acid in water and isopropanol solution, and heating in a high-pressure reaction kettle to obtain a precursor. And calcining the precursor material in a tubular furnace to obtain MnO @ C. For the same precursor, the porous carbon material can be obtained by changing the calcination temperature and carrying out acid treatment, and the porous carbon material can be applied to the negative electrode and the positive electrode of the lithium-ion hybrid capacitor.
(5) In the invention, when the cathode material is prepared by the same precursor, N is preferred 2 And the atmosphere can cause N permeation at a higher temperature, so that the electrical property of the hybrid capacitor is further improved.
Drawings
FIG. 1 is SEM and TEM morphology images of MnO @ C obtained in example 1 of the preparation method of the positive and negative electrode matching material of the lithium ion hybrid capacitor of the present invention.
Fig. 2 is SEM and TEM morphology images of a PC obtained in example 1 of the method for preparing a positive-negative electrode matching material for a lithium ion hybrid capacitor of the present invention.
FIG. 3 is a CV curve of MnO @ C// PC device obtained in example 1 of the method for preparing a positive and negative electrode matching material for a lithium ion hybrid capacitor of the present invention.
FIG. 4 shows a lithium ion mixture according to the present inventionPreparation method of cathode and anode matching material of hybrid capacitor 5Ag of MnO @ C// PC device obtained in example 1 -1 The cycle stability of the following.
FIG. 5 shows the rate capacity of MnO @ C// PC device obtained in example 1 of the method for preparing a positive and negative electrode matching material for a lithium ion hybrid capacitor of the present invention.
Detailed Description
The patent relates to a preparation method and application of a positive and negative electrode matching material of a lithium ion hybrid capacitor. The experimental details will be fully and clearly described below in connection with the present patent disclosure and specific examples so as to enable those skilled in the art to better understand the present invention.
The electrode materials prepared in the following examples were applied and tested for performance by the following methods: half cells were assembled to evaluate the electrochemical performance of mno @ c and PC materials, where the counter and reference electrodes were lithium sheets and the electrolyte was 1M LiPF in EC/DEC (1 6 . The lithium ion hybrid capacitor is assembled with MnO @ C as a negative electrode and PC as a positive electrode.
Preparing an electrode: a homogeneous slurry was formed by dispersing 10% acetylene black, 80% active material, and 10% Polytetrafluoroethylene (PVDF) in a N-methyl pyrrolidone (NMP) solution. The above slurry was coated on a copper foil and dried in an oven. Then preparing single electrode PC according to the above steps, adding acetylene black, and finally coating on aluminum foil.
Electrochemical performance measurement process: cyclic Voltammetry (CV) testing was performed on an electrochemical workstation (CHI 760E). Constant current charge and discharge performance and cycle stability were studied on a LAND battery tester (CT 2001A).
The invention provides a preparation method of a positive and negative electrode matching material of a lithium ion hybrid capacitor, which comprises the following steps:
step 1: 0.2-0.8 g of manganese chloride tetrahydrate (MnCl) 2 ·4H 2 O) and 1.0 to 1.5g of nitrosotriacetic acid (SNA) are dissolved in a mixed solution of ultrapure water and isopropanol with the volume ratio of 1;
step 2: transferring the homogeneous solution obtained in the step 1 into an autoclave, sealing and keeping at 150-200 ℃ for 4-8 h, cooling to 25 ℃ after heating, and collecting a precursor through vacuum filtration;
and step 3: repeatedly washing the precursor obtained in the step 2 by using ultrapure water and ethanol, and drying the washed precursor in an oven at 80 ℃ overnight to obtain a precursor Mn-SNA complex, and dividing the precursor into two parts;
and 4, step 4: transferring one part of the precursor obtained in the step 3 into a corundum boat, calcining for 1-3 h in a tubular furnace at the temperature of 400-600 ℃, and cooling to room temperature after calcination is finished to obtain a MnO @ C material;
and 5: transferring the other part of the precursor obtained in the step 3 into a corundum boat, carbonizing the precursor for 1 to 3 hours at the temperature of between 700 and 900 ℃ in a tubular furnace, and cooling the precursor to room temperature after calcination;
step 6: and (3) treating the powder obtained in the step (5) by using 0.01-0.1M HF, and then repeatedly washing the powder by using ultrapure water and ethanol to obtain the porous carbon material (PC).
Example 1
The embodiment provides a preparation method of a positive and negative electrode matching material of a lithium ion hybrid capacitor, which comprises the following steps:
step 1: 0.6g of manganese chloride tetrahydrate (MnCl) 2 ·4H 2 O), 1.2g of nitrosotriacetic acid (SNA) is dissolved in a mixed solution of ultrapure water and isopropanol with the volume ratio of 1;
and 2, step: transferring the homogeneous solution obtained in the step 1 into an autoclave, sealing and keeping at 180 ℃ for 6 hours, cooling to 25 ℃ after heating, and carrying out vacuum filtration to collect a precursor;
and step 3: repeatedly washing the precursor obtained in the step 2 by using ultrapure water and ethanol, and drying the washed precursor in an oven at 80 ℃ overnight to obtain a precursor Mn-SNA complex, and dividing the precursor into two parts;
and 4, step 4: transferring one part of the precursor obtained in the step 3 into a corundum boat, calcining for 2h (Ar atmosphere) in a tube furnace at 500 ℃, and cooling to room temperature after calcination to obtain MnO @ C;
and 5: transferring the other part of the precursor obtained in the step 3 into a corundum boat and then placing the corundum boat in a tube furnaceCarbonizing at 800 deg.C for 2h (N) 2 Atmosphere), cooling to room temperature after calcination is finished;
and 6: treating the powder obtained in the step 5 with 0.05M HF to remove Mn, and then repeatedly washing with ultrapure water and ethanol to obtain a porous carbon material (PC);
when the matching material obtained in the embodiment is subjected to characterization and electrochemical performance test, the MnO @ C composite material and the porous carbon material are in a one-dimensional nanorod form and have porous structures. In FIG. 1, it can be seen that MnO @ C contains a large amount of MnO particles and is wrapped in a carbon shell. As can be seen in fig. 2, much of the MnO has been removed from the porous carbon material. The device MnO @ C// PC assembled by the obtained matching material has excellent energy storage performance, and the energy storage performance is 48Wkg -1 At a power density of 89Wh kg -1 Even at 18kW kg -1 Can maintain 45Wh kg under the power density -1 The energy density of (1). At 5Ag -1 The assembled MnO @ C// PC is subjected to a cycle stability test at the current density of (1), and the capacitance can still keep 88.2 percent of the initial value after 3000 cycles.
Example 2
The embodiment provides a preparation method of a positive and negative electrode matching material of a lithium ion hybrid capacitor, which comprises the following steps:
step 1: 0.7g of manganese chloride tetrahydrate (MnCl) 2 ·4H 2 O) and 1.2g of nitrosotriacetic acid (SNA) are dissolved in a mixed solution of ultrapure water and isopropanol in a volume ratio of 1;
and 2, step: transferring the homogeneous solution obtained in the step 1 into an autoclave, sealing and keeping at 180 ℃ for 6h, cooling to 25 ℃ after heating, and carrying out vacuum filtration to collect a precursor;
and step 3: repeatedly washing the precursor obtained in the step 2 by using ultrapure water and ethanol, and drying the washed precursor in an oven at 80 ℃ overnight to obtain a precursor Mn-SNA complex, and dividing the precursor into two parts;
and 4, step 4: transferring one part of the precursor obtained in the step 3 into a corundum boat, calcining for 2h (Ar atmosphere) in a tubular furnace at 500 ℃, and cooling to room temperature after the calcination is finished to obtain MnO @ C;
and 5: transferring the other part of the precursor obtained in the step 3 into a corundum boat to be carbonized for 2h (N) at 800 ℃ in a tube furnace 2 Atmosphere), cooling to room temperature after calcination is finished;
step 6: treating the powder obtained in the step 5 by using 0.05M HF, and then repeatedly washing the powder by using ultrapure water and ethanol to obtain a porous carbon material (PC);
the characterization and electrochemical performance test of the electrode material obtained in the embodiment are carried out, and the MnO @ C composite material and the porous carbon both present a one-dimensional nanorod form and have a porous structure. The obtained electrode material assembled device MnO @ C// PC has excellent energy storage performance at 45W kg -1 Shows 83Wh kg at power density -1 At an ultra-high energy density of 18kW kg -1 39Wh kg at power density -1 The energy density of (2). At 5Ag -1 The assembled MnO @ C// PC is subjected to a cycle stability test at the current density of (1), and the capacitance can still keep 87.0 percent of the initial value after 3000 cycles.
Example 3
The embodiment provides a preparation method of a positive and negative electrode matching material of a lithium ion hybrid capacitor, which comprises the following steps:
step 1: 0.6g of manganese chloride tetrahydrate (MnCl) 2 ·4H 2 O), 1.4g of nitrosotriacetic acid (SNA) is dissolved in a solution of ultrapure water and isopropanol in a volume ratio of 1;
step 2: transferring the homogeneous solution obtained in the step 1 into an autoclave, sealing and keeping at 180 ℃ for 6 hours, cooling to 25 ℃ after heating, and carrying out vacuum filtration to collect a precursor;
and step 3: repeatedly washing the precursor obtained in the step 2 by using ultrapure water and ethanol, and drying the washed precursor in an oven at 80 ℃ overnight to obtain a precursor Mn-SNA complex, and dividing the precursor into two parts;
and 4, step 4: transferring one part of the precursor obtained in the step 3 into a corundum boat, calcining for 2h (Ar atmosphere) in a tubular furnace at 500 ℃, and cooling to room temperature after the calcination is finished to obtain MnO @ C;
and 5: another precursor obtained in step 3The body is transferred into a corundum boat and carbonized for 2h (N) at 800 ℃ in a tube furnace 2 Atmosphere), cooling to room temperature after calcination is finished;
and 6: treating the powder obtained in the step 5 by using 0.05M HF, and then repeatedly washing the powder by using ultrapure water and ethanol to obtain a porous carbon material (PC);
when the electrode material obtained in the embodiment is subjected to characterization and electrochemical performance test, the MnO @ C composite material and the porous carbon are in a one-dimensional nanorod form and have porous structures. The obtained electrode material assembled device MnO @ C// PC has excellent energy storage performance, and the energy storage performance is 48W kg -1 Shows 85Wh kg at power density -1 At an ultra-high energy density of 18kW kg -1 41Wh kg at Power Density -1 The energy density of (1). At 5Ag -1 The assembled MnO @ C// PC is subjected to a cycle stability test at the current density of (1), and the capacitance can still keep 87.9 percent of the initial value after 3000 cycles.
Example 4
The embodiment provides a preparation method of a positive and negative electrode matching material of a lithium ion hybrid capacitor, which comprises the following steps:
step 1: 0.6g of manganese chloride tetrahydrate (MnCl) 2 ·4H 2 O) and 1.2g of nitrosotriacetic acid (SNA) are dissolved in a mixed solution of ultrapure water and isopropanol in a volume ratio of 1;
step 2: transferring the homogeneous solution obtained in the step 1 into an autoclave, sealing and keeping at 180 ℃ for 6 hours, cooling to 25 ℃ after heating, and carrying out vacuum filtration to collect a precursor;
and step 3: repeatedly washing the precursor obtained in the step 2 by using ultrapure water and ethanol, drying the washed precursor in an oven at the temperature of 80 ℃ overnight to obtain a precursor Mn-SNA complex, and dividing the precursor Mn-SNA complex into two parts;
and 4, step 4: transferring one part of the precursor obtained in the step 3 into a corundum boat, calcining for 2h (Ar atmosphere) in a tubular furnace at 550 ℃, and cooling to room temperature after the calcination is finished to obtain MnO @ C;
and 5: transferring the other part of the precursor obtained in the step 3 into a corundum boat to be carbonized for 2h (N) at 850 ℃ in a tube furnace 2 Atmosphere), cooling to room temperature after calcination is finished;
step 6: treating the powder obtained in the step 5 by using 0.05M HF, and then repeatedly washing the powder by using ultrapure water and ethanol to obtain a porous carbon material (PC);
the characterization and electrochemical performance test of the electrode material obtained in the embodiment are carried out, and the MnO @ C composite material and the porous carbon both present a one-dimensional nanorod form and have a porous structure. The obtained electrode material assembled device MnO @ C// PC has excellent energy storage performance, and the energy storage performance is 44W kg -1 Shows 80Wh kg at power density -1 At an ultra-high energy density of 18kW kg -1 38Wh kg at power density -1 The energy density of (1). At 5Ag -1 When the assembled MnO @ C// PC is subjected to a cycle stability test at the current density of (1), the capacitance can still maintain 87.6 percent of the initial value after 3000 cycles.
Example 5
The embodiment provides a preparation method of a positive and negative electrode matching material of a lithium ion hybrid capacitor, which comprises the following steps:
step 1: 0.6g of manganese chloride tetrahydrate (MnCl) 2 ·4H 2 O) and 1.2g of nitrosotriacetic acid (SNA) are dissolved in a mixed solution of ultrapure water and isopropanol in a volume ratio of 1;
step 2: transferring the homogeneous solution obtained in the step 1 into an autoclave, sealing and keeping at 180 ℃ for 6 hours, cooling to 25 ℃ after heating, and carrying out vacuum filtration to collect a precursor;
and step 3: repeatedly washing the precursor obtained in the step 2 by using ultrapure water and ethanol, drying the washed precursor in an oven at the temperature of 80 ℃ overnight to obtain a precursor Mn-SNA complex, and dividing the precursor Mn-SNA complex into two parts;
and 4, step 4: transferring one part of the precursor obtained in the step 3 into a corundum boat, calcining for 2h (Ar atmosphere) in a tubular furnace at 450 ℃, and cooling to room temperature after the calcination is finished to obtain MnO @ C;
and 5: transferring the other part of the precursor obtained in the step 3 into a corundum boat, and carbonizing the corundum boat for 2 hours at 750 ℃ in a tube furnace (N) 2 Atmosphere), cooling to room temperature after calcination is finished;
step 6: treating the powder obtained in the step 5 by using 0.05M HF, and then repeatedly washing the powder by using ultrapure water and ethanol to obtain a porous carbon material (PC);
when the electrode material obtained in the embodiment is subjected to characterization and electrochemical performance test, the MnO @ C composite material and the porous carbon are in a one-dimensional nanorod form and have porous structures. The obtained electrode material assembled device MnO @ C// PC has excellent energy storage performance, and the energy storage performance is 46W kg -1 Shows 82Wh kg at power density -1 At an ultra-high energy density of 18kW kg -1 40Wh kg at power density -1 The energy density of (1). At 5Ag -1 The assembled MnO @ C// PC is subjected to a cycle stability test at the current density of (1), and the capacitance can still keep 87.8 percent of the initial value after 3000 cycles.
Example 6
The steps of the preparation method of the positive-negative electrode matching material of the lithium-ion hybrid capacitor in this embodiment are the same as those of embodiment 1, except that the carbonization process in step 5 in this embodiment is performed in an Ar atmosphere. When the electrode material obtained in the embodiment is subjected to characterization and electrochemical performance tests, the MnO @ C composite material and the porous carbon material are in a one-dimensional nanorod form and have a porous structure. The obtained electrode material assembled device MnO @ C// PC has excellent energy storage performance, and the energy storage performance is 48W kg -1 Shows 85Wh kg at power density -1 Even at 18kW kg -1 Can maintain 41Wh kg under the power density -1 The energy density of (1). At 5Ag -1 The assembled MnO @ C// PC is subjected to a cycle stability test at the current density of (1), and the capacitance can still keep 82.3 percent of the initial value after 3000 cycles.
The invention is applicable to the prior art where nothing is said.

Claims (5)

1. A preparation method of a positive and negative electrode matching material of a lithium ion hybrid capacitor is characterized by comprising the following steps:
step 1: 0.2-0.8 g of manganese chloride tetrahydrate (MnCl) 2 ·4H 2 O), 1.0-1.5 g of nitroso-triacetic acid (SNA) in ultrapure water andin a solution with the volume ratio of isopropanol being 1;
and 2, step: transferring the homogeneous solution obtained in the step 1 into an autoclave, sealing and keeping at 150-200 ℃ for 4-8 h, cooling to 25 ℃ after heating, and collecting a precursor through vacuum filtration;
and step 3: repeatedly washing the precursor obtained in the step 2 by using ultrapure water and ethanol, and drying the washed precursor in an oven at 80 ℃ overnight to obtain a precursor Mn-SNA complex, and dividing the precursor into two parts;
and 4, step 4: transferring one part of the precursor obtained in the step 3 into a corundum boat, calcining for 1-3 h in a tubular furnace at 400-600 ℃ under the protective atmosphere, and cooling to room temperature after the calcination is finished to obtain a MnO @ C material;
and 5: transferring the other part of the precursor obtained in the step 3 into a corundum boat, carbonizing the corundum boat in a tube furnace at the temperature of 700-900 ℃ for 1-3 h under protective atmosphere, and cooling to room temperature after calcination;
and 6: and (4) treating the powder obtained in the step (5) by using 0.01-0.1M HF solution, and then repeatedly washing the powder by using ultrapure water and ethanol to obtain the porous carbon material (PC).
2. The method for preparing the positive-negative electrode matching material of the lithium ion hybrid capacitor as claimed in claim 1, wherein in the step 1, the manganese chloride tetrahydrate is 0.6g, and the nitrosotriacetic acid is 1.2g.
3. The method for preparing the positive-negative electrode matching material of the lithium ion hybrid capacitor as claimed in claim 1, wherein in the step 2, the temperature of the autoclave is 180 ℃, and the heat preservation time is 6 hours; in the step 4, the calcining temperature is 500 ℃, the heat preservation time is 2 hours, and the calcining is carried out under the Ar atmosphere; in the step 5, the calcining temperature is 800 ℃, the heat preservation time is 2 hours, and the protective atmosphere is N 2 Atmosphere; in step 6, the concentration of the HF solution was 0.05M.
4. The application of the positive and negative electrode matching material of the lithium ion hybrid capacitor is characterized in that the MnO @ C material and the porous carbon material (PC) obtained by the preparation method of any one of claims 1-3 are used, and the application process is as follows: first, 10% acetylene black, 80% MnO @ C material and 10% Polytetrafluoroethylene (PVDF) were dispersed in N-methylpyrrolidone (NMP) solution to form a uniform slurry, the slurry was coated on a copper foil and dried in an oven to obtain single electrode MnO @ C, acetylene black was added to a porous carbon material (PC), and finally coated on an aluminum foil to form single electrode PC.
5. The use according to claim 4, wherein the resulting matched material assembled device MnO @ C// PC retains more than 80% of its initial value after 3000 cycles, and the capacitor has high energy density, high power density and excellent stability.
CN202211069366.5A 2022-09-02 2022-09-02 Preparation method and application of positive and negative electrode matching material of lithium ion hybrid capacitor Pending CN115331978A (en)

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