CN110706941A - Preparation method of partially-metallized oxygen-deficient tin oxide supercapacitor positive electrode material - Google Patents
Preparation method of partially-metallized oxygen-deficient tin oxide supercapacitor positive electrode material Download PDFInfo
- Publication number
- CN110706941A CN110706941A CN201910995578.8A CN201910995578A CN110706941A CN 110706941 A CN110706941 A CN 110706941A CN 201910995578 A CN201910995578 A CN 201910995578A CN 110706941 A CN110706941 A CN 110706941A
- Authority
- CN
- China
- Prior art keywords
- tin oxide
- deficient
- electrode material
- oxygen
- nickel
- 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.)
- Granted
Links
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic 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
- H01G11/24—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
- H01G11/46—Metal oxides
-
- 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 partially-alloyed oxygen-deficient tin oxide supercapacitor positive electrode material, and belongs to the technical field of new energy material preparation and application. The anode material provided by the invention is composed of partial Sn-Ni alloyed oxygen-deficient nano porous particle tin oxide embedded in foamed nickel, can be directly used as a working electrode of a super capacitor, and has the advantages of large active substance loading capacity, good conductivity, large specific capacitance, good circulation stability and no toxicity or harm to a human body. According to the method, tin dioxide is used as a raw material, foam nickel is used as a current collector, tin dioxide slurry is firstly poured into the foam nickel, then a sample is dried in a drying box, and then high-temperature heat treatment is carried out in a vacuum tube furnace in a reducing atmosphere, so that the cathode material is finally obtained. The composition and the appearance of the anode material obtained by the method are controllable; the raw materials, equipment and process are particularly simple, the product yield is high, the cost is extremely low, the production process is safe and environment-friendly, and the method is suitable for large-scale production.
Description
Technical Field
The invention relates to a preparation method of a partially-alloyed oxygen-deficient tin oxide supercapacitor positive electrode material, and belongs to the technical field of new energy material preparation and application.
Background
The super capacitor is a novel energy storage device between the capacitor and the battery, and has the advantages of high power density, high charging speed, environmental friendliness, long cycle service life, high reliability and the like. The super capacitor can be divided into a double electric layer super capacitor and a pseudo capacitor super capacitor according to different energy storage mechanisms. Among them, the double layer capacitor stores energy by using a charge layer on an electrode/electrolyte interface, and its performance is mainly determined by the adsorption capacity of an electrode material, and such a material having excellent performance includes a carbon-based material having a large specific surface area, and the like. The pseudo-capacitance super capacitor stores energy by utilizing reversible electrochemical reaction between electrode materials and electrolyte, and the factors influencing the performance of the capacitor are many: the material is required to have high specific capacitance, good conductivity, long cycle life, high electrochemical oxidation/reduction rate and the like, and the excellent performance of the material currently comprises various transition metal oxides, conductive polymers and the like; secondly, the structure of the anode material requires large specific surface area of the material, active sites of active substances are fully exposed, and the structural stability is good, so that various nano-structure and porous structure materials and the like can be produced at the same time. In addition, the composition and structure of the negative electrode material, the composition and structure of the current collector, the electrolyte properties, and the contact conditions between the electrode material/current collector/electrolyte also have important influences on the performance of the supercapacitor. Particularly, although the number of active sites can be significantly increased by using the nanomaterial as an electrode material, the loading of the active substance on the electrode is low, but the area specific capacitance and the volume specific capacitance of the supercapacitor are seriously reduced, so that the cruising ability of the supercapacitor is influenced, and the supercapacitor can be widely applied to devices such as portable devices and large-scale integrated circuits.
In particular, among the numerous transition metal oxide cathode materials, tin dioxide (SnO)2) Has the advantages of low cost, no toxicity, no harm, good thermal stability and the like, and is a potential energy storage material. However, the tin dioxide has the defects of poor conductivity, serious agglomeration of nano structures, poor multiplying power performance of the capacitor and the like, so that the practical application of the tin dioxide as a high-performance pseudo-capacitance electrode material is hindered. In order to improve SnO2Electrochemical performance of electrode materials, materials scientists proposed: (1) can be in SnO2Constructing a heterostructure with other metal oxide nanostructures, and establishing an internal electric field in the sample; (2) high-conductivity carbon-based materials or conductive polymers and SnO can be selected2Nano-structured composite for improving SnO2The conductivity, specific surface area and even the final specific capacitance of the base electrode material; (3) SnO may be reacted2The composite material is compounded with metal oxide materials with high specific capacitance, such as manganese oxide, cobalt oxide, titanium oxide and the like, so as to improve the capacitance performance of the material.
In addition, the nano metal material has the advantages of high specific surface area, high energy density, good conductivity, good cycling stability and the like, and the nano porous metal material has rich active sites, so that the metal nano material or the porous material thereof is adopted as the active material and the current collector, and the nano porous metal material is an ideal electrode material of the super capacitor and has wide development prospect. Moreover, alloy materials of different kinds of metals applied to the super capacitor can often show better electrochemical performance, including improving the kind and efficiency of redox reaction, enhancing the specific capacity of electrode materials, and the like. Therefore, in recent years, research on the preparation and application of alloy materials has also received much attention (k.zhuo, et al.appl.surf.sci.,2014,322, 15-20).
Therefore, the invention provides a preparation method of the partially metallized oxygen-deficient tin oxide supercapacitor positive electrode material. According to the technology provided by the invention, tin dioxide is used as an electrochemical active material raw material, foam nickel is used as a current collector, tin dioxide slurry is firstly poured into the foam nickel, then a sample is dried in a drying box, and high-temperature heat treatment is carried out in a vacuum tube furnace in a reducing atmosphere, so that a partial Sn-Ni alloyed oxygen-deficient tin oxide sample embedded in the foam nickel is finally obtained. This tin oxide sample can be used directly as the working electrode (positive electrode) of a supercapacitor. According to the super capacitor anode material prepared by the method, the active substance is poured in the foam nickel, the loading capacity is large, the area specific capacitance and the volume specific capacitance of the capacitor are very high, the endurance capacity of the capacitor is strong, the volume of the capacitor can be smaller under the condition of the same capacitance, and the super capacitor anode material is more suitable for being used as a portable device and a large-scale integrated circuit; because the active substance particles are embedded in the foam nickel in a nano and porous form, the specific surface area of the material is large, the active sites are fully exposed, and the mass specific capacitance of the electrode is large; in the electrode material, the valence state of metal cations is rich, the electrochemical reaction is complex, and the material capacitance is high; the current collector of the electrode material is metal with excellent conductivity, the active substances are oxygen-deficient tin oxide with strong conductivity and newly-added Sn-Ni alloy with excellent conductivity, and the oxygen-deficient tin oxide and the newly-added Sn-Ni alloy are organically combined together through high-temperature heat treatment, so that the electrode material has good conductivity and is beneficial to the rapid transfer of charges; the active material particles and the gaps constructed by the foamed nickel in the electrode material provide buffer spaces for the volume expansion of electrochemical reaction caused by ion intercalation and deintercalation, so that the capacitor has good structural stability, and the electrode material has excellent cycling stability due to the existence of Ni alloy. In addition, the electrode material of the super capacitor is a tin oxide-based material, so that the super capacitor is non-toxic and harmless to human bodies; the obtained oxygen-deficient tin oxide nano-porous material has the advantages of high sample yield and controllable composition and appearance. In addition, the preparation method of the supercapacitor anode material provided by the invention has the advantages of simple raw materials, equipment and process, strong controllability of process and parameters, high product yield, extremely low cost, safe, clean and environment-friendly production process and suitability for large-scale production.
Disclosure of Invention
The invention aims to provide a partially metallized oxygen-deficient tin oxide supercapacitor positive electrode material. The super capacitor anode material is composed of partial Sn-Ni alloyed oxygen-deficient nano porous particle tin oxide embedded in foamed nickel. This tin oxide sample can be used directly as the working electrode (positive electrode) of a supercapacitor. The super capacitor anode material prepared by the method has large active substance loading capacity, high area specific capacitance and volume specific capacitance of the capacitor, strong capacitor endurance, smaller capacitor volume under the same capacitance condition, and is more suitable for being used as a portable device and a large-scale integrated circuit; because the active substance particles are embedded in the foam nickel in a nano and porous form, the specific surface area of the material is large, the active sites are fully exposed, and the mass specific capacitance of the electrode is large; in the electrode material, the valence state of metal cations is rich, the electrochemical reaction is complex, and the material capacitance is high; the current collector of the electrode material is metal with excellent conductivity, the active substances are oxygen-deficient tin oxide with strong conductivity and newly-added Sn-Ni alloy with excellent conductivity, and the oxygen-deficient tin oxide and the newly-added Sn-Ni alloy are organically combined together through high-temperature heat treatment, so that the electrode material has good conductivity and is beneficial to the rapid transfer of charges; the active material particles and the gaps constructed by the foamed nickel in the electrode material provide buffer spaces for the volume expansion of electrochemical reaction caused by ion intercalation and deintercalation, so that the capacitor has good structural stability, and the electrode material has excellent cycling stability due to the existence of Ni alloy. In addition, the electrode material of the super capacitor is a tin oxide-based material, so that the electrode material is non-toxic and harmless to human bodies.
The invention also aims to provide a corresponding preparation method of the partially alloyed oxygen-deficient tin oxide supercapacitor positive electrode material. The oxygen-deficient tin oxide nano porous material obtained by the method has high sample yield and controllable composition and appearance; meanwhile, the method has the advantages of simple raw materials, equipment and process, strong controllability of process and parameters, high product yield, extremely low cost, safe, clean and environment-friendly production process and suitability for large-scale production.
In order to achieve the aim, the invention provides a partially alloyed oxygen-deficient tin oxide supercapacitor positive electrode material which is characterized in that the supercapacitor positive electrode material is composed of partially Sn-Ni alloyed oxygen-deficient nano porous particle tin oxide embedded in foamed nickel. The super capacitor anode material has the advantages of large active substance load capacity, rich metal cation valence, large specific surface area, full active site exposure, good conductivity, large electrode mass specific capacitance and area specific capacitance in terms of volume specific capacitance, good circulation stability, no toxicity or harm to human bodies, and is an excellent super capacitor anode material.
The preparation method of the partially alloyed oxygen-deficient tin oxide supercapacitor positive electrode material is characterized in that tin dioxide is used as a raw material, foam nickel is used as a current collector, tin dioxide slurry is poured into the foam nickel, then a sample is dried in a drying box, and high-temperature heat treatment is carried out in a vacuum tube furnace in a reducing atmosphere, so that a partially Sn-Ni alloyed oxygen-deficient tin oxide sample embedded in the foam nickel is obtained finally.
The preparation method of the partially alloyed oxygen-deficient tin oxide supercapacitor positive electrode material provided by the invention comprises the following steps and contents:
(1) taking a proper amount of tin dioxide powder, dispersing the tin dioxide powder in absolute ethyl alcohol, and magnetically stirring for 30-60min to obtain a uniformly dispersed suspension.
(2) And pouring the obtained tin dioxide suspension into clean foamed nickel, and drying in a drying oven for later use.
(3) Placing the sample obtained in the step (2) at the bottom of an alumina crucible, and surrounding the sample with some pre-oxidized polyacrylonitrile or epoxy resin; and then placing the crucible in a vacuum tube furnace, heating under the protection of inert atmosphere, cooling to room temperature along with the furnace, and taking out to obtain the partially alloyed oxygen-deficient tin oxide supercapacitor positive electrode material.
In the preparation method, the tin dioxide powder in the step (1) is analytically pure nano powder or submicron powder.
In the preparation method, the dosage ratio of the absolute ethyl alcohol to the tin dioxide powder in the step (1) is 100mL (20-40 g).
In the preparation method, when the tin dioxide is dispersed in the absolute ethyl alcohol in the step (1), the tin dioxide is magnetically stirred until a milky thick turbid liquid is obtained.
In the above preparation method, the cleaning method of the foamed nickel sheet in the step (2) is: taking a piece of foam nickel, sequentially placing the foam nickel in acetone and absolute ethyl alcohol solution, respectively carrying out ultrasonic cleaning for 15-20min, and then drying.
In the above preparation method, the method for pouring the tin dioxide slurry in the nickel foam in the step (2) is one of injection and gel injection.
In the preparation method, the drying temperature of the sample in the drying oven in the step (2) is 80-90 ℃, and the heat preservation time is 3-24 h.
In the above production method, the thermal reduction atmosphere in the step (3) is provided by thermal decomposition of one of pre-oxidized polyacrylonitrile or epoxy resin; the preoxidized polyacrylonitrile or epoxy resin is fiber or powder with mass of 2-12g/cm2A nickel foam.
In the above preparation method, the inert atmosphere in the step (3) is provided by high purity nitrogen or argon, and the purity is more than 99.99 vol.%.
In the preparation method, the heat treatment temperature in the step (3) is 300-.
The invention is characterized in that:
(1) the super capacitor anode material is composed of partial Sn-Ni alloyed oxygen-deficient nano porous particle tin oxide embedded in foamed nickel. The main component of the composite is oxygen-deficient tin oxide and contains a small amount of Ni-Sn alloy to form a uniform composite.
(2) In the process of preparing the partially alloyed oxygen-deficient tin oxide supercapacitor material, tin dioxide is used as a raw material, foam nickel is used as a current collector, tin dioxide slurry is firstly poured into the foam nickel, then a sample is dried in a drying box, and high-temperature heat treatment is carried out in a vacuum tube furnace in a reducing atmosphere, so that a partially Sn-Ni alloyed oxygen-deficient tin oxide sample embedded in the foam nickel is finally obtained.
The invention has the advantages that:
(1) the tin oxide sample can be directly used as a positive electrode material of a super capacitor. The super capacitor anode material prepared by the method has large active substance loading capacity, high area specific capacitance and volume specific capacitance of the capacitor, strong capacitor endurance, smaller capacitor volume under the same capacitance condition, and is more suitable for being used as a portable device and a large-scale integrated circuit; because the active substance particles are embedded in the foam nickel in a nano and porous form, the specific surface area of the material is large, the active sites are fully exposed, and the mass specific capacitance of the electrode is large; in the electrode material, the valence state of metal cations is rich, the electrochemical reaction is complex, and the material capacitance is high; the current collector of the electrode material is metal with excellent conductivity, the active substances are oxygen-deficient tin oxide with strong conductivity and newly-added Sn-Ni alloy with excellent conductivity, and the oxygen-deficient tin oxide and the newly-added Sn-Ni alloy are organically combined together through high-temperature heat treatment, so that the electrode material has good conductivity and is beneficial to the rapid transfer of charges; the active material particles and the gaps constructed by the foamed nickel in the electrode material provide buffer spaces for the volume expansion of electrochemical reaction caused by ion intercalation and deintercalation, so that the capacitor has good structural stability, and the electrode material has excellent cycling stability due to the existence of Ni alloy. In addition, the electrode material of the super capacitor is a tin oxide-based material, so that the electrode material is non-toxic and harmless to human bodies.
(2) The oxygen-deficient tin oxide nano porous material obtained by the method has high sample yield and controllable composition and appearance; meanwhile, the method has the advantages of simple raw materials, equipment and process, strong controllability of process and parameters, high product yield, extremely low cost, safe, clean and environment-friendly production process and suitability for large-scale production.
(3) The raw materials of the technology of the invention are nontoxic, harmless, simple and easily available.
(4) The thermal reduction of the tin oxide is realized by reducing gas generated by the thermal decomposition of pre-oxidized polyacrylonitrile or epoxy resin organic matters, the traditional hydrogen thermal reduction is not needed, and the method is clean, environment-friendly and greatly improved in safety.
Drawings
FIG. 1 is a scanning electron micrograph of a partially alloyed oxygen deficient tin oxide supercapacitor positive electrode material prepared in example 4 of the present invention taken under a scanning electron microscope
FIG. 2 is a high-power scanning electron micrograph of the partially alloyed anoxic type tin oxide supercapacitor positive electrode material prepared in example 4 of the present invention
FIG. 3 shows the X-ray diffraction pattern and the analysis result of the partial alloying oxygen deficient tin oxide super capacitor anode material prepared in example 4 of the present invention
FIG. 4 is a cyclic voltammogram of the partially alloyed anoxic tin oxide supercapacitor positive electrode material prepared in example 4 of the present invention
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
The invention provides a partially alloyed oxygen-deficient tin oxide supercapacitor positive electrode material which is characterized by being composed of partially Sn-Ni alloyed oxygen-deficient nano porous particle tin oxide embedded in foamed nickel. The super capacitor anode material has the advantages of large active substance load capacity, rich metal cation valence, large specific surface area, full active site exposure, good conductivity, large electrode mass specific capacitance and area specific capacitance in terms of volume specific capacitance, good circulation stability, no toxicity or harm to human bodies, and is an excellent super capacitor anode material.
The preparation method of the partially alloyed oxygen-deficient tin oxide supercapacitor positive electrode material is characterized in that tin dioxide is used as a raw material, foam nickel is used as a current collector, tin dioxide slurry is poured into the foam nickel, then a sample is dried in a drying box, and high-temperature heat treatment is carried out in a vacuum tube furnace in a reducing atmosphere, so that a partially Sn-Ni alloyed oxygen-deficient tin oxide sample embedded in the foam nickel is obtained finally.
The preparation method of the partially alloyed oxygen-deficient tin oxide supercapacitor positive electrode material provided by the invention comprises the following steps and contents:
(1) 20-40g of analytically pure tin dioxide nano powder or submicron powder is taken and dispersed in 100mL of absolute ethyl alcohol, and is magnetically stirred for 30-60min to obtain uniformly dispersed suspension.
(2) Then the obtained tin dioxide suspension is poured into clean foam nickel by an injection method or a gel injection method, and is dried in a drying oven for standby.
(3) Placing the sample obtained in the step (2) at the bottom of an alumina crucible, and surrounding the sample with some pre-oxidized polyacrylonitrile or epoxy resin; and then placing the crucible in a vacuum tube furnace, heating under the protection of inert atmosphere of high-purity nitrogen or argon gas of more than 99.99 vol.%, cooling to room temperature along with the furnace, and taking out to obtain the partially alloyed oxygen-deficient tin oxide supercapacitor positive electrode material.
(4) The cleaning method of the foam nickel sheet in the step (2) comprises the following steps: taking a piece of foam nickel, sequentially placing the foam nickel in acetone and absolute ethyl alcohol solution, respectively carrying out ultrasonic cleaning for 15-20min, and then drying.
(5) In the step (2), the drying temperature of the sample in the drying oven is 80-90 ℃, and the heat preservation time is 3-24 h.
(6) In the step (3), the pre-oxidized polyacrylonitrile or epoxy resin is fiber or powder with a mass of 2-12g/cm2A nickel foam.
(7) The heat treatment temperature in the step (3) is 300-.
The obtained partially alloyed oxygen deficient tin oxide supercapacitor positive electrode material is a white to gray solid in appearance. Under a scanning electron microscope, many nanoporous particles were observed embedded in the nickel foam. X-ray diffraction analysis shows that the material mainly comprises oxygen-deficient tin oxide and contains a small amount of Ni-Sn alloy. The cyclic-voltammetry test shows that the sample has obvious redox peaks, and the electrochemical performance of the sample is excellent.
In a word, the technology can be used for preparing the high-performance partially-alloyed oxygen-deficient tin oxide supercapacitor positive electrode material.
Example (b): 30g of commercially available analytically pure tin dioxide submicron powder is taken and dispersed in 100mL of absolute ethyl alcohol, and the mixture is magnetically stirred for 30min to obtain a uniformly dispersed suspension. Then, taking a piece of foam nickel sheet with the size of 1cm multiplied by 1.5cm, sequentially placing the foam nickel sheet in acetone and absolute ethyl alcohol solution, respectively carrying out ultrasonic cleaning for 15min, and drying for later use. 5mL of tin dioxide suspension is poured into the clean piece of foamed nickel by an injection method, and the piece of foamed nickel is kept warm for 3h in a drying oven at 80 ℃. Then, the obtained sample was placed at the bottom of an alumina crucible, and 4g of pre-oxidized polyacrylonitrile fiber was surrounded around the sample; and then placing the crucible in a vacuum tube furnace, preserving the heat for 30-360min at the temperature of 300-800 ℃ under the protection of inert atmosphere of high-purity nitrogen or argon of more than 99.99 vol.%, and finally cooling along with the furnace to room temperature and taking out to obtain the partially alloyed oxygen-deficient tin oxide supercapacitor anode material.
The typical low-power scanning electron microscope photo of the obtained sample is shown in figure 1, the high-power scanning electron microscope photo is shown in figure 2, a plurality of nano-porous particles can be observed to be embedded in the foamed nickel, and the material maintains the porous structure of the foamed nickel; this material is composed mainly of oxygen-deficient tin oxide and contains a small amount of Ni — Sn alloy (see fig. 3); when this sample was used directly as the supercapacitor positive electrode, its cyclic voltammogram exhibited a strong redox peak (see fig. 4), indicating that the sample had excellent capacitive properties (see table 1). Different from the traditional electrode material, the electrode material prepared by the invention has super-strong electrochemical cycle performance, and the specific capacity of the electrode material can be continuously enhanced along with the increase of cycle times, and reaches more than twenty times of the initial capacity.
TABLE 1
Claims (5)
1. The partially-alloyed oxygen-deficient tin oxide supercapacitor positive electrode material is characterized by being composed of partial Sn-Ni-alloyed oxygen-deficient nano porous particle tin oxide embedded in foamed nickel.
2. The preparation method of the partially alloyed oxygen-deficient tin oxide supercapacitor positive electrode material according to claim 1, characterized in that tin dioxide is used as a raw material, foam nickel is used as a current collector, tin dioxide slurry is firstly poured into the foam nickel, then the sample is dried in a drying box, and then high-temperature heat treatment is carried out in a vacuum tube furnace in a reducing atmosphere, so that a partially Sn-Ni alloyed oxygen-deficient tin oxide sample embedded in the foam nickel is finally obtained; the method comprises the following steps:
(1) taking 20-40g of analytically pure tin dioxide nano powder or submicron powder, dispersing the analytically pure tin dioxide nano powder or submicron powder in 100mL of absolute ethyl alcohol, and magnetically stirring for 30-60min to obtain uniformly dispersed suspension;
(2) then, the obtained tin dioxide suspension is poured into clean foamed nickel by an injection method or a gel injection method, and is dried in a drying oven for later use;
(3) placing the sample obtained in the step (2) at the bottom of an alumina crucible, and surrounding the sample with some pre-oxidized polyacrylonitrile or epoxy resin; and then placing the crucible in a vacuum tube furnace, heating under the protection of inert atmosphere of high-purity nitrogen or argon gas of more than 99.99 vol.%, cooling to room temperature along with the furnace, and taking out to obtain the partially alloyed oxygen-deficient tin oxide supercapacitor positive electrode material.
3. The preparation method according to claim 2, wherein the ratio of the absolute ethyl alcohol to the tin dioxide powder in the step (1) is 100mL (20-40 g); when the stannic oxide is dispersed in the absolute ethyl alcohol, the mixture is magnetically stirred until a milky thick turbid liquid is obtained.
4. The method according to claim 2, wherein the tin dioxide slurry is poured into the nickel foam in step (2) by one of injection and gel casting; the temperature of the sample dried in the drying oven is 80-90 ℃, and the heat preservation time is 3-24 h.
5. The method according to claim 2, wherein the thermal reducing atmosphere in the step (3) is provided by thermal decomposition of one of pre-oxidized polyacrylonitrile or epoxy resin; the preoxidized polyacrylonitrile or epoxy resin is fiber or powder with mass of 2-12g/cm2Nickel foam; the inert atmosphere is provided by high-purity nitrogen or argon, and the purity is over 99.99 vol.%; the heat treatment temperature is 300-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910995578.8A CN110706941B (en) | 2019-10-18 | 2019-10-18 | Preparation method of partially-alloyed oxygen-deficient tin oxide supercapacitor positive electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910995578.8A CN110706941B (en) | 2019-10-18 | 2019-10-18 | Preparation method of partially-alloyed oxygen-deficient tin oxide supercapacitor positive electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110706941A true CN110706941A (en) | 2020-01-17 |
| CN110706941B CN110706941B (en) | 2020-11-24 |
Family
ID=69201738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910995578.8A Expired - Fee Related CN110706941B (en) | 2019-10-18 | 2019-10-18 | Preparation method of partially-alloyed oxygen-deficient tin oxide supercapacitor positive electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110706941B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326233A (en) * | 2000-05-25 | 2001-12-12 | 默克专利股份有限公司 | Induced positive electrode material for electrochemical cell |
| JP2011190164A (en) * | 2010-02-17 | 2011-09-29 | Ishihara Sangyo Kaisha Ltd | Composite containing tin oxide and tin compound with oxygen deficiency and production method thereof |
| CN105552320A (en) * | 2015-12-11 | 2016-05-04 | 湘潭大学 | Foam nickel substrate Sn/SnO/SnO2 layered three-dimensional porous negative electrode material and preparation method thereof |
| CN106564892A (en) * | 2016-11-04 | 2017-04-19 | 华中科技大学 | Method for conducting oxygen vacancy introduction on transition metal oxide in intrinsic modification manner |
-
2019
- 2019-10-18 CN CN201910995578.8A patent/CN110706941B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326233A (en) * | 2000-05-25 | 2001-12-12 | 默克专利股份有限公司 | Induced positive electrode material for electrochemical cell |
| JP2011190164A (en) * | 2010-02-17 | 2011-09-29 | Ishihara Sangyo Kaisha Ltd | Composite containing tin oxide and tin compound with oxygen deficiency and production method thereof |
| CN105552320A (en) * | 2015-12-11 | 2016-05-04 | 湘潭大学 | Foam nickel substrate Sn/SnO/SnO2 layered three-dimensional porous negative electrode material and preparation method thereof |
| CN106564892A (en) * | 2016-11-04 | 2017-04-19 | 华中科技大学 | Method for conducting oxygen vacancy introduction on transition metal oxide in intrinsic modification manner |
Non-Patent Citations (1)
| Title |
|---|
| JINYUN LIU,ET AL.: ""Hydrothermal Fabrication of Three-Dimensional Secondary Battery Anodes"", 《ADV. MATER.》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110706941B (en) | 2020-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xia et al. | Freestanding Co3O4 nanowire array for high performance supercapacitors | |
| CN111453726A (en) | Nitrogen-doped porous carbon material and preparation method and application thereof | |
| CN108054020B (en) | Preparation method and application of nitrogen-doped carbon particle/graphitized carbon-nitrogen composite material | |
| CN107293715B (en) | A kind of lithium-sulphur cell positive electrode S/CNT-CeO2The preparation method of composite material | |
| CN108922790A (en) | A kind of manganese dioxide/N doping porous carbon composite preparation method and application of sodium ion insertion | |
| CN112850708A (en) | Preparation method and application of nitrogen-doped porous carbon material with high specific surface area | |
| CN112017868B (en) | Mesoporous hollow carbon micron cage material and preparation method and application thereof | |
| CN110808179A (en) | Nitrogen-oxygen co-doped biomass hard carbon material and preparation method and application thereof | |
| CN106450241A (en) | Titanium nitride/carbon nitride/graphene oxide composite nano-material and preparation method thereof | |
| Luo et al. | Multifunctional sandwich-structured double-carbon-layer modified SnS nanotubes with high capacity and stability for Li-ion batteries | |
| CN114267838A (en) | Sodium ion battery composite positive electrode material and preparation method thereof | |
| CN110078130B (en) | Preparation method of hollow-structure iron-based compound and application of hollow-structure iron-based compound as cathode material of supercapacitor | |
| CN108550824A (en) | A kind of high-capacity battery cathode material preparation method | |
| CN110060873B (en) | Hollow biochar sphere-based nickel sulfide nanorod supercapacitor and preparation method thereof | |
| CN108963237B (en) | Preparation method of sodium ion battery negative electrode material | |
| Luo et al. | Graphene-controlled FeSe nanoparticles embedded in carbon nanofibers for high-performance potassium-ion batteries | |
| CN113644269B (en) | Preparation method of nitrogen-doped hard carbon material, product and application thereof | |
| CN108598403A (en) | The forming method of lithium ion battery transiton metal binary oxides negative material | |
| CN112951619A (en) | Iron oxide @ manganese dioxide core-shell structure material and preparation and application thereof | |
| CN110706941B (en) | Preparation method of partially-alloyed oxygen-deficient tin oxide supercapacitor positive electrode material | |
| CN114804039B (en) | Carbon matrix composite vanadium nitride nano array and preparation method and application thereof | |
| CN110444406A (en) | A kind of preparation method of fast activating three-dimensional Ni-C nano material as energy storage electrode material | |
| CN110767460B (en) | Preparation method of partially alloyed tin oxide nanorod array supercapacitor positive electrode material | |
| CN115520861A (en) | Method for rapidly synthesizing graphite by utilizing multi-physical-field coupling effect and application | |
| Ma et al. | Ni–Co bimetallic sulfide coated with reduced graphene oxide and carbon for high-capacitance supercapacitor |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20201124 Termination date: 20211018 |