CN113436905B - Preparation method of carbon/nickel oxide composite electrode material - Google Patents

Preparation method of carbon/nickel oxide composite electrode material Download PDF

Info

Publication number
CN113436905B
CN113436905B CN202110709694.6A CN202110709694A CN113436905B CN 113436905 B CN113436905 B CN 113436905B CN 202110709694 A CN202110709694 A CN 202110709694A CN 113436905 B CN113436905 B CN 113436905B
Authority
CN
China
Prior art keywords
nickel
nano
cellulose
carbon
electrode material
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.)
Active
Application number
CN202110709694.6A
Other languages
Chinese (zh)
Other versions
CN113436905A (en
Inventor
卿彦
吴义强
姜丽丽
田翠花
许瀚
李蕾
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.)
Central South University of Forestry and Technology
Original Assignee
Central South University of Forestry and Technology
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 Central South University of Forestry and Technology filed Critical Central South University of Forestry and Technology
Priority to CN202110709694.6A priority Critical patent/CN113436905B/en
Publication of CN113436905A publication Critical patent/CN113436905A/en
Application granted granted Critical
Publication of CN113436905B publication Critical patent/CN113436905B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
    • 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
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

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

Abstract

The invention discloses a preparation method of a carbon/nickel oxide composite electrode material, which comprises the following steps: (1) Fully stirring, dissolving and mixing the nano-cellulose suspension, the chitosan solution and the metal nickel salt to obtain nano-cellulose/metal nickel ion hydrogel; (2) Freezing and vacuum freeze-drying the nano-cellulose/metallic nickel ion hydrogel to obtain nano-cellulose/metallic nickel ion aerogel; (3) Carrying out high-temperature pyrolysis treatment on the nano-cellulose/metallic nickel ion aerogel in a protective atmosphere to obtain carbon/metallic nickel; (4) And carrying out electro-oxidation activation treatment on the carbon/metallic nickel to obtain the carbon/nickel oxide composite electrode material. The invention utilizes bamboo/wood-based nano-cellulose as a carbon source structure framework and introduces chitosan to finally prepare the nano-cellulose derived carbon-embedded nickel oxide electrode material with excellent electrochemical properties.

Description

Preparation method of carbon/nickel oxide composite electrode material
Technical Field
The invention belongs to the field of battery materials, and particularly relates to a preparation method of an electrode material.
Background
The rapid development of contemporary society has led to an increasing demand for energy storage devices and equipment. Various high efficiency energy storage systems, such as lithium ion batteries, nickel zinc batteries, and supercapacitors, are widely used in portable electronic devices and hybrid electric vehicles. In these energy storage systems, the electrode material plays an important role, and the electrode material is the main part for energy storage and conversion, and the performance of the electrode material directly affects the performance of the whole energy storage device. Nickel oxide is a commonly used electrode material in many energy storage systems because it undergoes a reversible redox reaction under alkaline conditions, in which there is a transfer and transport of charge that creates capacitance. However, nickel oxide has the problems of poor conductivity, easy agglomeration, small specific surface area, few active sites and the like, so that the nickel oxide has smaller capacitance and poorer stability and rate capability. In order to improve the capacitance and stability of the nickel oxide electrode, it is very meaningful to find a green sustainable and economically advantageous substrate material for improving the nickel oxide electrode.
At present, in the existing research technology, some materials with special structures are combined with nickel oxide to prepare novel electrode materials, so that the defects of the nickel oxide are overcome, and the electrochemical performance of the electrode is improved. However, the preparation process of these electrode materials is complicated and tedious, and intermediates involved in the process are difficult to repeat, so that the development of the electrode has no universality and sustainability and is difficult to further expand the production.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings mentioned in the background technology, and provide a preparation method of a carbon/nickel oxide composite electrode material which has a three-dimensional network porous structure and shows good electrochemical performance. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of a carbon/nickel oxide composite electrode material comprises the following steps:
(1) Fully stirring, dissolving and mixing the bamboo/wood-based nano cellulose suspension, the chitosan solution and the metal nickel salt to obtain nano cellulose/metal nickel ion hydrogel;
(2) Freezing and vacuum freeze-drying the nano-cellulose/metallic nickel ion hydrogel obtained in the step (1) to obtain nano-cellulose/metallic nickel ion aerogel;
(3) Carrying out high-temperature pyrolysis treatment on the nano-cellulose/metallic nickel ion aerogel obtained in the step (2) in a protective atmosphere to obtain carbon/metallic nickel;
(4) And (4) carrying out electro-oxidation activation treatment on the carbon/metallic nickel obtained in the step (3) to obtain the carbon/nickel oxide composite electrode material.
In the preparation method, the nano-cellulose suspension is preferably a bamboo/wood-based nano-cellulose suspension, and the mass concentration of the bamboo/wood-based nano-cellulose suspension is 0.2 to 1.0wt%; and controlling the mass ratio of the bamboo/wood-based nanocellulose to the metal nickel ions in the bamboo/wood-based nanocellulose suspension to be (0.5-4): 1. the bamboo/wood-based nano-cellulose has the advantages of easily available raw materials, wide sources and more convenient extraction and preparation. The concentration of the bamboo/wood-based nanocellulose is an important factor influencing the structure of the aerogel, the nano dispersion density of nickel and nickel oxide is regulated and controlled by controlling the using amount of the nanocellulose, and the proper concentration of the bamboo/wood-based nanocellulose is favorable for constructing a good electrode structure. The relative content of the bamboo/wood-based nano-cellulose and the metal nickel salt has important influence on the performance of the electrode material; if the content of the bamboo/wood-based nanocellulose is low, the content of the easily agglomerated metal oxide is relatively high, relatively more metal oxide is not easily dispersed, and the specific surface area of the nickel oxide is still small, so that the electrochemical material transmission and exchange are not facilitated; however, the content of the bamboo/wood-based nanocellulose is too high, and although the metal oxide is uniformly dispersed, the components are relatively less, so that abundant active sites cannot be formed on the nanocellulose-derived carbon skeleton, and the nickel oxide active sites are less distributed, so that higher capacitance cannot be achieved.
In the preparation method, the mass concentration of the chitosan solution is preferably 1 to 5wt%; and controlling the mass ratio of chitosan to metal nickel ions in the chitosan solution to be (2 to 4): 1, more preferably 2.84:1. the chitosan has abundant active amino and hydroxyl, and the stable combination of the nano-cellulose and nickel ions is facilitated by adding a small amount of the chitosan. The chitosan solution has certain viscosity, when the dosage of the chitosan is excessive, the mixed solution is difficult to stir, and the formation of the nano-cellulose/metallic nickel ion hydrogel is not facilitated; if the chitosan is too little, the auxiliary connection function of the chitosan between the nano-cellulose and the metal nickel salt is lacked, and the formation of hydrogel is also not facilitated.
The carbon source in the electrode material prepared by the invention is mainly derived from nano bamboo/wood-based nano cellulose and chitosan, the former is used for constructing a three-dimensional carbon skeleton structure, the latter is used for assisting nano metal nickel particles to be more uniformly and firmly dispersed and embedded in the three-dimensional carbon skeleton, and both are carbon sources but supplement each other to form a synergistic effect to construct a composite electrode material with better performance. The chitosan cannot be simply considered as a carbon source for forming a carbon skeleton, and the obtained electrode material has better effect compared with the single nano bamboo/wood-based nano cellulose by adopting the chitosan. In order to ensure the function of chitosan, the dosage of chitosan also needs to be matched with the nano-cellulose and the metal nickel salt.
In the above preparation method, preferably, the metal nickel salt includes one or more of nickel nitrate, nickel sulfate and nickel chloride.
In the above production method, the stirring speed is preferably 500 to 800rpm, and the stirring time is preferably 3 to 5hours.
In the above production method, preferably, the freezing temperature is controlled to be-60 to-50 ℃ and the freezing time is controlled to be 4 to 6h; the vacuum freeze drying is carried out for 36 to 48h under vacuum at-60 to-50 ℃. Under the action of vacuum freeze drying, the hydrogel is successfully converted into aerogel, and the process is a basis for constructing a three-dimensional network porous carbon skeleton by using the nanocellulose.
In the preparation method, preferably, the high-temperature pyrolysis treatment is carried out at the temperature of 700-900 ℃ for 1-2h, the protective atmosphere is nitrogen, and the flow rate of the nitrogen is 0.12-0.18L.min -1 . The high-temperature pyrolysis is the key for converting the nano-cellulose into the carbon material, the carbonization temperature is too low, and the graphitization degree of the electrode material is low, so that the electron transmission is not facilitated; when the carbonization temperature is too high, the structure of the carbon material is damaged, and the electrochemical performance of the electrode material is also affected.
In the above preparation method, preferably, the carbon/metallic nickel is used to prepare a transition metal battery electrode plate, and then is subjected to electro-oxidation activation treatment, and the preparation method for preparing a transition metal battery electrode plate by using the carbon/metallic nickel comprises the following steps:
(1) Mixing carbon/metallic nickel, acetylene black and PVDF according to a mass ratio of 8:1:1, mixing, adding an ethanol solution, and grinding for 30min to prepare electrode slurry;
(2) Coating the electrode slurry obtained in the step (1) on foamed nickel and drying in vacuum to obtain a precursor of an electrode plate of the transition metal battery;
(3) And (3) tabletting the precursor of the transition metal battery electrode plate obtained in the step (2) under a tabletting machine to obtain the transition metal battery electrode plate.
In the preparation method, the drying temperature is controlled to be 80 to 100 ℃ and the drying time is controlled to be 8 to 10h when the materials are dried in vacuum; and (3) controlling the pressure of the tabletting machine to be 10-20MPa during tabletting, and controlling the tabletting time to be 3-5min.
In the preparation method, preferably, the electro-oxidation activation treatment is carried out in a three-electrode system, activation is carried out by adopting a constant voltage method, the electrolyte is a potassium hydroxide solution during activation, the oxidation voltage is controlled to be 1 to 2V, and the sensitivity is set to be 1.0e -1 The oxidation time is 100 to 300s, and the activation times is 10 to 15. The purpose of electro-oxidative activation is to successfully convert nickel metal sites in the electrode material into nickel oxide active sites resulting in high capacitance. The above-mentioned technological parameters of electrooxidation treatment can ensure the smooth operation of the above-mentioned process. Based on good dispersion and firm embedding of metal active sites in the electrode material, the invention is suitable for complete oxidation, does not need to regulate and control the proportion of nickel/nickel oxide, and is suitable for simplified treatment of expanded production.
The invention adopts bamboo/wood-based nano-cellulose with rich sources as a carbon source substrate material to carry out nano-scale dispersion and embedding on nickel oxide, thereby preparing the high-performance electrode material with the three-dimensional layered porous network. The nano-cellulose has rich hydroxyl groups and good biocompatibility, and under the condition of introducing chitosan, the nano-cellulose and metal nickel ions are more fully combined, so that uniform and stable bamboo/wood-based nano-cellulose/nickel ion mixed hydrogel is formed; after vacuum freeze drying, the hydrogel is converted into aerogel, carbon/metallic nickel is generated after high-temperature carbonization, and finally the carbon/nickel oxide composite electrode material is generated after electrooxidation activation. Based on the dispersion and embedment effect of the nanocellulose on the nickel oxide, the nickel oxide has good dispersibility, and the electrode material has larger specific surface area which is beneficial to the material transmission and conversion of the electrochemical reaction (the large specific surface area is mainly benefited by a three-dimensional network porous structure formed by the nanocellulose in the freeze drying process); meanwhile, the electrode material also has abundant active sites so as to obtain high capacitance (the abundant active sites are mainly uniform nano metal oxide particles formed under the dispersion action of nano cellulose); in addition, the nano-cellulose is successfully converted into graphitized carbon in the high-temperature process, so that the good conductivity of the electrode material is improved, and the electron transmission in the reaction is promoted to improve the rate capability of the electrode material.
Compared with the prior art, the invention has the advantages that:
1. the invention utilizes bamboo/wood-based nanocellulose as a carbon source structure skeleton to provide embedded points for nickel oxide and disperse the nickel oxide in a nano-scale manner; the bamboo/wood-based nanocellulose-derived three-dimensional carbon skeleton not only improves good conductivity, but also prevents nickel oxide from agglomerating, and greatly improves the capacitance performance, the cycle stability and the rate capability of the electrode material.
2. According to the invention, the structural characteristics of bamboo/nano-cellulose are utilized, chitosan is introduced, nano-cellulose and nickel ions are directly coupled, the preparation process is simplified, and nano-metal nickel particles are more uniformly and firmly dispersed and embedded in a three-dimensional carbon skeleton by the chitosan, so that an excellent nano-cellulose derived carbon embedded nickel oxide electrode material is prepared.
3. The preparation method has the advantages of simple process, strong operability and amplification, and can expand the realization of industrialization; the preparation process is environment-friendly and low in energy consumption, and great economic benefits are achieved; the experimental material has wide source and low cost, and is beneficial to the sustainable development of the research and development of energy storage materials.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention, the drawings used in the embodiments or technical solutions in the prior art are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a macroscopic view of the composite electrode material precursor prepared in example 1 (fig. 1 (a) is a bamboo nanocellulose/nickel ion aerogel, and fig. 1 (b) is carbon/metallic nickel).
Fig. 2 is a microscopic view of the electrode material prepared in example 1.
Fig. 3 is a graph showing the result of constant current charge and discharge test of the electrode material prepared in example 1.
Fig. 4 is a graph showing the results of cyclic voltammetry tests on the electrode material prepared in example 1.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a preparation method of a carbon/nickel oxide composite electrode material comprises the following steps:
(1) Mixing 100g of bamboo-based nano-cellulose with the mass concentration of 0.5wt%, 12.5g of 5wt% chitosan solution and 3.75mmol of nickel nitrate hexahydrate, and then uniformly stirring the mixture on a magnetic stirrer to obtain nano-cellulose/nickel ion hydrogel, wherein the stirring speed is 800rmp, and the stirring time is 4 hours;
(2) Putting the nano-cellulose/nickel ion hydrogel obtained in the step (1) into a mould, and putting the mould into a cold trap for freezing at the temperature of minus 60 ℃ for 4 hours; then carrying out vacuum freeze drying in a freeze dryer at the freezing temperature of-60 ℃ for 36 hours, and demolding to obtain the nano-cellulose/nickel ion aerogel;
(3) Placing the nano-cellulose/nickel ion aerogel obtained in the step (2) in an atmosphere tube furnace, and performing high-temperature pyrolysis under the protection of nitrogen atmosphere, wherein the temperature is 700 ℃, the time is 2 hours, the heating rate is 10 ℃/min, and the gas flow rate is 0.12L.min -1 Obtaining carbon/metallic nickel;
(4) Preparing the carbon/metallic nickel obtained in the step (3) into an electrode plate, wherein the method for preparing the electrode plate comprises the following steps:
(1) mixing the carbon/metal nickel electrode material and acetylene black PVDF according to the mass ratio of 8:1:1, mixing, adding an ethanol solution, and grinding for 30min to prepare electrode slurry;
(2) coating the electrode slurry obtained in the step (1) on foamed nickel and drying in vacuum to obtain a transition metal battery electrode plate, wherein the drying temperature is controlled at 90 ℃ and the drying time is 8 hours;
(3) tabletting the transition metal battery electrode slice obtained in the step (2) under a tablet press, wherein the pressure intensity of the tablet press is 10MPa, and the tabletting time is 5min;
(5) Performing electro-oxidation activation on the electrode slice obtained in the step (4) in a three-electrode system, and activating by adopting a constant voltage method, wherein the electrolyte is potassium hydroxide solution during activation, the oxidation voltage is controlled to be 1V, and the sensitivity is set to be 1.0e -1 The oxidation time was 200s, and the number of activations was 12.
The macroscopic view of the composite electrode material prepared in this example is shown in fig. 1, and it can be known from the figure that the electrode material still maintains a good aerogel form after high-temperature carbonization, and the shrinkage is small, which ensures the stability of the microstructure of the electrode material. As shown in fig. 2, it is known that the nickel nanoparticles are uniformly dispersed and embedded in the carbon network skeleton formed by the bamboo-based nanocellulose, which is beneficial to the rapid response of the electrochemical reaction. The electrochemical performance of the electrode material is tested, and as can be seen from the constant current discharge curve in fig. 3 and the cyclic voltammetry curve in fig. 4, the electrochemical performance of the electrode material in this embodiment is better, and the specific capacitance of the prepared electrode material is 731F/g.
Example 2:
a preparation method of a carbon/nickel oxide composite electrode material comprises the following steps:
(1) Mixing 100g of bamboo-based nano-cellulose with the mass concentration of 0.8wt%, 12.5g of 5wt% chitosan solution and 3.75mmol of nickel nitrate hexahydrate, and then uniformly stirring on a magnetic stirrer to obtain nano-cellulose/nickel ion hydrogel, wherein the stirring speed is 800rmp, and the stirring time is 4 hours;
(2) Putting the nano-cellulose/nickel ion hydrogel obtained in the step (1) into a mould, and putting the mould into a cold trap for freezing at the temperature of minus 60 ℃ for 4 hours; then carrying out vacuum freeze drying in a freeze dryer at the freezing temperature of-60 ℃ for 36 hours, and demoulding to obtain the nano cellulose/nickel ion aerogel;
(3) Placing the nano-cellulose/nickel ion aerogel obtained in the step (2) in an atmosphere tube furnace, and performing high-temperature pyrolysis under the protection of nitrogen atmosphere, wherein the temperature is 700 ℃, the time is 2 hours, the heating rate is 10 ℃/min, and the gas flow rate is 0.12L.min -1 Obtaining carbon/metallic nickel;
(4) Preparing the carbon/metallic nickel obtained in the step (3) into an electrode plate, wherein the method for preparing the electrode plate comprises the following steps:
(1) mixing the carbon/metal nickel electrode material and acetylene black PVDF according to the mass ratio of 8:1:1, mixing, adding an ethanol solution, and grinding for 30min to prepare electrode slurry;
(2) coating the electrode slurry obtained in the step (1) on foamed nickel and drying in vacuum to obtain a transition metal battery electrode plate, wherein the drying temperature is controlled at 90 ℃ and the drying time is 8 hours;
(3) tabletting the transition metal battery electrode slice obtained in the step (2) under a tablet press, wherein the pressure intensity of the tablet press is 10MPa, and the tabletting time is 5min;
(5) Performing electro-oxidation activation on the electrode slice obtained in the step (4) in a three-electrode system, and activating by adopting a constant voltage method, wherein the electrolyte is potassium hydroxide solution during activation, the oxidation voltage is controlled to be 2V, and the sensitivity is set to be 1.0e -1 The oxidation time was 200s, and the number of activations was 12.
The specific capacitance of the electrode material prepared in this example was 674F/g.
Example 3:
a preparation method of a carbon/nickel oxide composite electrode material comprises the following steps:
(1) Mixing 100g of bamboo-based nano-cellulose with the mass concentration of 0.2wt%, 12.5g of 5wt% chitosan solution and 3.75mmol of nickel nitrate hexahydrate, and then uniformly stirring the mixture on a magnetic stirrer to obtain nano-cellulose/nickel ion hydrogel, wherein the stirring speed is 600rmp, and the stirring time is 4 hours;
(2) Putting the nano-cellulose/nickel ion hydrogel obtained in the step (1) into a mould, and putting the mould into a cold trap for freezing at the temperature of minus 60 ℃ for 4 hours; then carrying out vacuum freeze drying in a freeze dryer at the freezing temperature of-60 ℃ for 36 hours, and demoulding to obtain the nano cellulose/nickel ion aerogel;
(3) Placing the nano-cellulose/nickel ion aerogel obtained in the step (2) in an atmosphere tube furnace, and performing high-temperature pyrolysis under the protection of nitrogen atmosphere, wherein the temperature is 700 ℃, the time is 2 hours, the heating rate is 10 ℃/min, and the gas flow rate is 0.12L.min -1 Obtaining carbon/metallic nickel;
(4) Preparing the carbon/metallic nickel obtained in the step (3) into an electrode plate, wherein the method for preparing the electrode plate comprises the following steps:
(1) mixing the carbon/metal nickel electrode material and acetylene black PVDF according to the mass ratio of 8:1:1, mixing, adding an ethanol solution, and grinding for 30min to prepare electrode slurry;
(2) coating the electrode slurry obtained in the step (1) on foamed nickel and drying in vacuum to obtain a transition metal battery electrode plate, wherein the drying temperature is controlled at 90 ℃ and the drying time is 8 hours;
(3) tabletting the transition metal battery electrode slice obtained in the step (2) under a tablet press, wherein the pressure intensity of the tablet press is 10MPa, and the tabletting time is 5min;
(5) Performing electro-oxidation activation on the electrode slice obtained in the step (4) in a three-electrode system, and activating by adopting a constant voltage method, wherein the electrolyte is potassium hydroxide solution during activation, the oxidation voltage is controlled to be 1V, and the sensitivity is set to be 1.0e -1 The oxidation time was 200s, and the number of activations was 12.
The specific capacitance of the electrode material prepared in this example was 363F/g.
Example 4:
a preparation method of a carbon/nickel oxide composite electrode material comprises the following steps:
(1) Mixing 100g of bamboo-based nano-cellulose with the mass concentration of 0.2wt%, 15g of 5wt% chitosan solution and 3.75mmol of nickel nitrate hexahydrate, and then placing the mixture on a magnetic stirrer to be uniformly stirred to obtain nano-cellulose/nickel ion hydrogel, wherein the stirring speed is 800rmp, and the stirring time is 4 hours;
(2) Putting the nano-cellulose/nickel ion hydrogel obtained in the step (1) into a mould, and putting the mould into a cold trap for freezing at the temperature of minus 60 ℃ for 4 hours; then carrying out vacuum freeze drying in a freeze dryer at the freezing temperature of-60 ℃ for 36 hours, and demoulding to obtain the nano cellulose/nickel ion aerogel;
(3) Putting the nano-cellulose/nickel ion aerogel obtained in the step (2) into an atmosphere tube furnace, and carrying out high-temperature pyrolysis under the protection of nitrogen atmosphere, wherein the temperature is 700 ℃, the time is 2h, the heating rate is 10 ℃/min, and the gas flow rate is 0.12L.min -1 To obtain carbon/metallic nickel;
(4) Preparing the carbon/metallic nickel obtained in the step (3) into an electrode plate, wherein the method for preparing the electrode plate comprises the following steps:
(1) mixing the carbon/metal nickel electrode material and acetylene black PVDF according to the mass ratio of 8:1:1, mixing, adding an ethanol solution, and grinding for 30min to prepare electrode slurry;
(2) coating the electrode slurry obtained in the step (1) on foamed nickel and drying in vacuum to obtain a transition metal battery electrode plate, wherein the drying temperature is controlled at 90 ℃ and the drying time is 8 hours;
(3) tabletting the transition metal battery electrode plate obtained in the step (2) under a tablet press, wherein the pressure intensity of the tablet press is 10MPa, and the tabletting time is 5min;
(5) Performing electro-oxidation activation on the electrode slice obtained in the step (4) in a three-electrode system, and activating by adopting a constant voltage method, wherein the electrolyte is a potassium hydroxide solution during activation, the oxidation voltage is controlled to be 2V, and the sensitivity is set to be 1.0e -1 The oxidation time was 200s, and the number of activations was 12.
The specific capacitance of the electrode material prepared in this example was 210F/g.
Example 5:
a preparation method of a carbon/nickel oxide composite electrode material comprises the following steps:
(1) Mixing 100g of bamboo-based nano-cellulose with the mass concentration of 0.2wt%, 7.5g of 5wt% chitosan solution and 3.75mmol of nickel nitrate hexahydrate, and then uniformly stirring on a magnetic stirrer to obtain nano-cellulose/nickel ion hydrogel, wherein the stirring speed is 600rmp, and the stirring time is 4 hours;
(2) Putting the nano-cellulose/nickel ion hydrogel obtained in the step (1) into a mould, and putting the mould into a cold trap for freezing at the temperature of minus 60 ℃ for 4 hours; then carrying out vacuum freeze drying in a freeze dryer at the freezing temperature of-60 ℃ for 36 hours, and demoulding to obtain the nano cellulose/nickel ion aerogel;
(3) Placing the nano-cellulose/nickel ion aerogel obtained in the step (2) in an atmosphere tube furnace, and performing high-temperature pyrolysis under the protection of nitrogen atmosphere, wherein the temperature is 700 ℃, the time is 2 hours, the heating rate is 10 ℃/min, and the gas flow rate is 0.12L.min -1 Obtaining carbon/metallic nickel;
(4) Preparing the carbon/metallic nickel obtained in the step (3) into an electrode slice, wherein the method for preparing the electrode slice comprises the following steps:
(1) mixing the carbon/metal nickel electrode material and acetylene black PVDF according to the mass ratio of 8:1:1, mixing, adding an ethanol solution, and grinding for 30min to prepare electrode slurry;
(2) coating the electrode slurry obtained in the step (1) on foamed nickel and drying in vacuum to obtain a transition metal battery electrode plate, wherein the drying temperature is controlled at 90 ℃ and the drying time is 8 hours;
(3) tabletting the transition metal battery electrode slice obtained in the step (2) under a tablet press, wherein the pressure intensity of the tablet press is 10MPa, and the tabletting time is 5min;
(5) Performing electro-oxidation activation on the electrode slice obtained in the step (4) in a three-electrode system, and activating by adopting a constant voltage method, wherein the electrolyte is a potassium hydroxide solution during activation, the oxidation voltage is controlled to be 1V, and the sensitivity is set to be 1.0e -1 The oxidation time was 300s, and the number of activations was 12.
The specific capacitance of the electrode material prepared in this example was 377F/g.
Comparative example 1:
this comparative example is different from example 1 in that no bamboo-based nanocellulose was added in step (1).
The main difference of the comparative example from the above example is that the nickel oxide electrode has no supporting and dispersing function of the nanocellulose, the specific surface area of the electrode is small, the electrode is not beneficial to contact with the electrolyte, and the nickel oxide agglomeration is serious, so that rapid electrochemical response cannot occur, and high capacitance is generated.
The specific capacitance of the electrode material prepared in this comparative example was 110F/g.
Comparative example 2:
this comparative example is different from example 1 in that no chitosan solution was added in step (1).
The specific capacitance of the electrode material prepared in this comparative example was 349F/g.
Comparative example 3:
this comparative example is different from example 1 in that the temperature of the high-temperature pyrolysis was controlled to 1000 ℃.
The specific capacitance of the electrode material prepared in this comparative example was 251F/g.

Claims (10)

1. A preparation method of a carbon/nickel oxide composite electrode material is characterized by comprising the following steps:
(1) Fully stirring, dissolving and mixing the nano-cellulose suspension, the chitosan solution and the metal nickel salt to obtain nano-cellulose/metal nickel ion hydrogel;
(2) Freezing and vacuum freeze-drying the nano-cellulose/metallic nickel ion hydrogel obtained in the step (1) to obtain nano-cellulose/metallic nickel ion aerogel;
(3) Carrying out high-temperature pyrolysis treatment on the nano-cellulose/metallic nickel ion aerogel obtained in the step (2) in a protective atmosphere to obtain carbon/metallic nickel;
(4) Performing electro-oxidation activation treatment on the carbon/metallic nickel obtained in the step (3) to obtain a carbon/nickel oxide composite electrode material;
the nano-cellulose suspension is bamboo/wood-based nano-cellulose suspension, and the mass ratio of the bamboo/wood-based nano-cellulose to the metal nickel ions in the bamboo/wood-based nano-cellulose suspension is controlled to be (0.5 to 4): 1;
controlling the mass ratio of chitosan to metal nickel ions in the chitosan solution to be (2 to 4): 1.
2. the preparation method according to claim 1, wherein the mass concentration of the bamboo/wood-based nanocellulose suspension is 0.2 to 1.0wt%.
3. The method according to claim 1, wherein the chitosan solution has a mass concentration of 1 to 5wt%.
4. The preparation method according to claim 1, wherein the mass ratio of chitosan to metallic nickel ions in the chitosan solution is controlled to be 2.84:1.
5. the method of claim 1, wherein the metallic nickel salt comprises one or more of nickel nitrate, nickel sulfate, and nickel chloride.
6. The production method according to any one of claims 1 to 5, wherein the freezing temperature is controlled to be-60 to-50 ℃ and the freezing time is controlled to be 4 to 6 hours; the vacuum freeze drying is to dry the mixture for 36 to 48h under vacuum at-60 to-50 ℃.
7. The method according to any one of claims 1 to 5, wherein the high-temperature pyrolysis treatment is carried out at a temperature of 700 to 900 ℃ for 1 to 2h under a protective atmosphere of nitrogen at a flow rate of 0.12 to 0.18L.min -1 。
8. The preparation method of any one of claims 1 to 5, wherein the carbon/metallic nickel is used for preparing a transition metal battery electrode plate, and then is subjected to electro-oxidation activation treatment, and the preparation method of the transition metal battery electrode plate by using the carbon/metallic nickel comprises the following steps:
(1) Mixing carbon/metallic nickel, acetylene black and PVDF according to a mass ratio of 8:1:1, mixing, adding an ethanol solution, and grinding to prepare electrode slurry;
(2) Coating the electrode slurry obtained in the step (1) on foamed nickel and drying in vacuum to obtain a precursor of the electrode plate of the transition metal battery;
(3) And (3) tabletting the precursor of the transition metal battery electrode plate obtained in the step (2) under a tabletting machine to obtain the transition metal battery electrode plate.
9. The method according to claim 8, wherein the drying temperature is controlled to be 80 to 100 ℃ and the drying time is controlled to be 8 to 10 hours; and (3) controlling the pressure of a tabletting machine to be 10 to 20MPa during tabletting, and controlling the tabletting time to be 3 to 5min.
10. The preparation method according to any one of claims 1 to 5, wherein the electro-oxidative activation treatment is carried out in a three-electrode system, the activation is carried out by adopting a constant voltage method, and the electrolyte is a potassium hydroxide solution during the activationThe oxidation voltage was controlled to be 1 to 2V, and the sensitivity was set to 1.0e -1 The oxidation time is 100 to 300s, and the activation times is 10 to 15 times.
CN202110709694.6A 2021-06-25 2021-06-25 Preparation method of carbon/nickel oxide composite electrode material Active CN113436905B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110709694.6A CN113436905B (en) 2021-06-25 2021-06-25 Preparation method of carbon/nickel oxide composite electrode material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110709694.6A CN113436905B (en) 2021-06-25 2021-06-25 Preparation method of carbon/nickel oxide composite electrode material

Publications (2)

Publication Number Publication Date
CN113436905A CN113436905A (en) 2021-09-24
CN113436905B true CN113436905B (en) 2022-10-04

Family

ID=77754582

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110709694.6A Active CN113436905B (en) 2021-06-25 2021-06-25 Preparation method of carbon/nickel oxide composite electrode material

Country Status (1)

Country Link
CN (1) CN113436905B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113998688B (en) * 2021-11-03 2023-07-14 安徽工程大学 Porous carbon nanomaterial based on chitosan colloid particles and preparation method and application thereof
CN114835103A (en) * 2022-06-01 2022-08-02 襄阳市大学科技园发展有限公司 Preparation method and application of carbon and nickel oxide composite electrode material

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009155417A1 (en) * 2008-06-18 2009-12-23 Board Of Trustees Of The University Of Arkansas Microwave-assisted synthesis of carbon and carbon-metal composites from lignin, tannin and asphalt derivatives and applications of same
JPWO2013153916A1 (en) * 2012-04-09 2015-12-17 昭和電工株式会社 Electrochemical device current collector manufacturing method, electrochemical device electrode manufacturing method, electrochemical device current collector, electrochemical device, and coating liquid for producing electrochemical device current collector
CN106268679B (en) * 2016-09-22 2019-06-18 海安县中山合成纤维有限公司 A kind of preparation method of chitosan nano fiber element base composite spherical adsorbent material
CN109433154B (en) * 2018-11-26 2021-01-29 中国科学院生态环境研究中心 Three-dimensional reticular graphene aerogel, and preparation method and application thereof
CN109360738B (en) * 2018-12-17 2020-11-10 中南林业科技大学 Preparation method of nickel/nickel oxide loaded nano wood fiber carbon aerogel electrode
CN111153448B (en) * 2019-12-27 2022-07-15 中南林业科技大学 Preparation method and application of bamboo/wood-based nano-cellulose limited transition metal oxide electrode material

Also Published As

Publication number Publication date
CN113436905A (en) 2021-09-24

Similar Documents

Publication Publication Date Title
CN108767260B (en) Carbon-coated FeP hollow nano-electrode material and preparation method and application thereof
CN109801792B (en) Preparation method and application of carbon-coated iron oxide electrode material
CN108598414B (en) Amorphous zinc oxide/carbon composite lithium ion battery cathode material and preparation method thereof
CN111362254A (en) Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material
CN107464938B (en) Molybdenum carbide/carbon composite material with core-shell structure, preparation method thereof and application thereof in lithium air battery
CN113436905B (en) Preparation method of carbon/nickel oxide composite electrode material
CN107959006A (en) A kind of lignin-base hard carbon/carbon nano tube compound material and preparation method thereof and the application in lithium ion battery negative material
CN111193014B (en) Cobaltosic oxide-nitrogen doped carbon/carbon nanocage composite material with eggshell-yolk structure and preparation method and application thereof
CN113948681B (en) Biomass-based hard carbon compound composite material and preparation method and application thereof
CN107579250B (en) Composite carbon material conductive agent
CN111063872A (en) Silicon-carbon negative electrode material and preparation method thereof
CN111153448A (en) Preparation method and application of bamboo/wood-based nano-cellulose limited transition metal oxide electrode material
CN114725366B (en) Preparation method of niobium-titanium oxide negative electrode material for lithium ion battery
CN113066965A (en) MXene-silicon composite anode material, battery containing MXene-silicon composite anode material, and preparation method and application of MXene-silicon composite anode material
CN109360738B (en) Preparation method of nickel/nickel oxide loaded nano wood fiber carbon aerogel electrode
CN108963237B (en) Preparation method of sodium ion battery negative electrode material
CN109786769B (en) Carbon-supported noble metal oxide bifunctional catalyst and preparation method and application thereof
CN110589823A (en) Shaddock peel porous carbon material and preparation method and application thereof
CN112786869B (en) Preparation method of ferric oxide/spiral carbon nanofiber composite anode material
CN117558889A (en) Low-cost composite lithium ion battery anode material, preparation method and application thereof
CN110600710B (en) Iron sulfide-carbon composite material and preparation method thereof, lithium ion battery negative electrode material, lithium ion battery negative electrode piece and lithium ion battery
CN109817908B (en) Silicon-carbon composite material, preparation method thereof and lithium ion battery
CN110970599B (en) Graphene-based composite negative electrode material, preparation method thereof and lithium ion battery
CN114944480B (en) Preparation method of honeycomb porous tin-carbon composite material
CN111082027A (en) Preparation method of biomass carbon lithium ion battery 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
GR01 Patent grant
GR01 Patent grant