CN110706941B - Preparation method of partially-alloyed oxygen-deficient tin oxide supercapacitor positive electrode material - Google Patents
Preparation method of partially-alloyed oxygen-deficient tin oxide supercapacitor positive electrode material Download PDFInfo
- Publication number
- CN110706941B CN110706941B CN201910995578.8A CN201910995578A CN110706941B CN 110706941 B CN110706941 B CN 110706941B CN 201910995578 A CN201910995578 A CN 201910995578A CN 110706941 B CN110706941 B CN 110706941B
- Authority
- CN
- China
- Prior art keywords
- tin oxide
- electrode material
- deficient
- nickel
- preparation
- 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.)
- Expired - Fee Related
Links
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910001887 tin oxide Inorganic materials 0.000 title claims abstract description 55
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 230000002950 deficient Effects 0.000 title claims abstract description 46
- 239000001301 oxygen Substances 0.000 title claims abstract description 46
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 46
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 103
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 51
- 239000006260 foam Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 21
- 229910020938 Sn-Ni Inorganic materials 0.000 claims abstract description 16
- 229910008937 Sn—Ni Inorganic materials 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000003822 epoxy resin Substances 0.000 claims description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 239000011858 nanopowder Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 41
- 239000000463 material Substances 0.000 abstract description 23
- 239000010405 anode material Substances 0.000 abstract description 16
- 239000013543 active substance Substances 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 8
- 238000011068 loading method Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 231100000956 nontoxicity Toxicity 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 description 32
- 239000000956 alloy Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229910045601 alloy Inorganic materials 0.000 description 8
- 238000003487 electrochemical reaction Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 231100000252 nontoxic Toxicity 0.000 description 4
- 230000003000 nontoxic effect Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000007783 nanoporous material Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 229910018100 Ni-Sn Inorganic materials 0.000 description 2
- 229910018532 Ni—Sn Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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
-
- 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, 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
- H01G11/46—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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Ceramic Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
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 (4)
1. The preparation method of the partially-alloyed oxygen-deficient tin oxide supercapacitor positive electrode material is characterized in that the supercapacitor positive electrode material is composed of partial Sn-Ni-alloyed oxygen-deficient nano porous particle tin oxide embedded in foamed nickel; the preparation method comprises the steps of taking tin dioxide as a raw material and foam nickel as a current collector, firstly pouring tin dioxide slurry into the foam nickel, then drying a sample in a drying box, and then carrying out high-temperature heat treatment in a vacuum tube furnace in a reducing atmosphere to finally obtain a partial Sn-Ni alloyed oxygen-deficient tin oxide sample embedded in the foam nickel; the method comprises the following steps:
(1) dispersing analytically pure tin dioxide nano powder or submicron powder in absolute ethyl alcohol, and magnetically stirring for 30-60min to obtain uniformly dispersed suspension;
(2) then 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 epoxy resin or pre-oxidized polyacrylonitrile; 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.
2. The preparation method according to claim 1, 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.
3. The method according to claim 1, 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.
4. The method of claim 1, wherein the reducing atmosphere is provided by thermal decomposition of one of an epoxy resin or pre-oxidized polyacrylonitrile; the epoxy resin or pre-oxidized polyacrylonitrile 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 CN110706941A (en) | 2020-01-17 |
CN110706941B true 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) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20230011946A (en) * | 2020-05-20 | 2023-01-25 | 니폰 가가쿠 고교 가부시키가이샤 | Conductive particle, conductive material and connection structure using the same |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10025762A1 (en) * | 2000-05-25 | 2001-11-29 | Merck Patent Gmbh | Reduced anode material in electrochemical cells |
JP5676907B2 (en) * | 2010-02-17 | 2015-02-25 | 石原産業株式会社 | Method for treating lithium titanate particles |
CN105552320B (en) * | 2015-12-11 | 2019-03-08 | 湘潭大学 | A kind of Ni-based Sn/SnO/SnO of foam2Three-dimensional porous negative electrode material of stratiform and preparation method thereof |
CN106564892B (en) * | 2016-11-04 | 2018-08-21 | 华中科技大学 | A method of intrinsic modified introducing Lacking oxygen is carried out to transition metal oxide |
-
2019
- 2019-10-18 CN CN201910995578.8A patent/CN110706941B/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN110706941A (en) | 2020-01-17 |
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 | |
Luo et al. | Graphene-controlled FeSe nanoparticles embedded in carbon nanofibers for high-performance potassium-ion batteries | |
CN108963237B (en) | Preparation method of sodium ion battery negative electrode material | |
CN113644269B (en) | Preparation method of nitrogen-doped hard carbon material, product and application thereof | |
CN110706941B (en) | Preparation method of partially-alloyed oxygen-deficient tin oxide supercapacitor positive electrode material | |
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 | |
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 | |
CN115692032A (en) | CuCo 2 O 4 Preparation method and application of @ MoNi-LDH composite material | |
CN115520861A (en) | Method for rapidly synthesizing graphite by utilizing multi-physical-field coupling effect and application |
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 |