CN113629257A - Preparation method of three-dimensional carbon fiber based multi-layer coating structure composite material of seawater dissolved oxygen battery - Google Patents
Preparation method of three-dimensional carbon fiber based multi-layer coating structure composite material of seawater dissolved oxygen battery Download PDFInfo
- Publication number
- CN113629257A CN113629257A CN202110673038.5A CN202110673038A CN113629257A CN 113629257 A CN113629257 A CN 113629257A CN 202110673038 A CN202110673038 A CN 202110673038A CN 113629257 A CN113629257 A CN 113629257A
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- composite material
- temperature
- dissolved oxygen
- 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.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 82
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 54
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 54
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 54
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 41
- 239000001301 oxygen Substances 0.000 title claims abstract description 41
- 239000013535 sea water Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000011248 coating agent Substances 0.000 title claims abstract description 27
- 238000000576 coating method Methods 0.000 title claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000011159 matrix material Substances 0.000 claims abstract description 14
- 238000003763 carbonization Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 80
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 48
- 229910052799 carbon Inorganic materials 0.000 claims description 47
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 44
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 40
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 40
- 229910002588 FeOOH Inorganic materials 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 30
- 239000012498 ultrapure water Substances 0.000 claims description 30
- 238000004140 cleaning Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 24
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- 229920000128 polypyrrole Polymers 0.000 claims description 20
- 230000035484 reaction time Effects 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 10
- 238000007605 air drying Methods 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- 238000005530 etching Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000003760 magnetic stirring Methods 0.000 claims description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 10
- 235000011152 sodium sulphate Nutrition 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003892 spreading Methods 0.000 claims description 5
- 230000007480 spreading Effects 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 239000007772 electrode material Substances 0.000 abstract description 9
- 230000009467 reduction Effects 0.000 abstract description 9
- 239000000446 fuel Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000007774 longterm Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000005234 chemical deposition Methods 0.000 abstract description 2
- 238000005554 pickling Methods 0.000 abstract 1
- 238000002203 pretreatment Methods 0.000 abstract 1
- 230000009471 action Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- -1 magnesium-silver halide Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/49—Oxides or hydroxides of elements of Groups 8, 9,10 or 18 of the Periodic Table; Ferrates; Cobaltates; Nickelates; Ruthenates; Osmates; Rhodates; Iridates; Palladates; Platinates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method of a three-dimensional carbon fiber multi-layered coating structure composite material of a seawater dissolved oxygen battery, and relates to a pretreatment method of a three-dimensional flexible carbon fiber brush, an electrocatalytic oxygen reduction composite material with a Fe @ C-N coating structure, a preparation method of the electrocatalytic oxygen reduction composite material, and the like. When in preparation, high-temperature heat treatment and acid pickling pretreatment of the matrix are firstly carried out to remove impurities on the surface of the carbon fiber matrix and improve the stability of the material; then, a convenient chemical deposition method is adopted to obtain the composite material with the multilayer coating structure; and finally, carrying out high-temperature vacuum carbonization treatment to obtain the composite electrocatalytic electrode material with high stability and high catalytic activity. The three-dimensional flexible composite electrode material has the advantages of low price, convenient preparation method, large specific surface area, high oxygen reduction catalytic activity, good stability and the like, can improve the energy output of a seawater dissolved oxygen battery and improve the long-term stability of the seawater dissolved oxygen battery, and also lays a foundation for the research and practical application of fuel batteries such as seawater semi-fuel batteries, metal-air batteries and the like.
Description
Technical Field
The invention relates to a composite material for a seawater dissolved oxygen battery and a preparation method thereof, belonging to the field of chemical energy application, in particular to a composite electrode material with a Fe @ C-N coating structure of a three-dimensional flexible carbon fiber substrate, which can be used for continuously and stably supplying power for a very long time for various low-power ocean monitoring and detecting devices such as an offshore lifesaving signal lamp, a sonar buoy, an underwater unmanned carrier, a submarine earthquake observation instrument and the like in an ocean environment after being built with an alloy material with high activity and high negative potential into a primary seawater semi-fuel battery.
Background
At present, the mature chemical sources used by marine equipment are various types, such as lead-acid batteries, cadmium-nickel batteries, proton exchange membrane batteries, lithium ion batteries and the like, but the mature chemical sources used by marine equipment have some problems when used for underwater power: the lead-acid battery and the cadmium-nickel battery have low specific energy (about 40 Wh/kg on average) and short cycle life; silver-zinc batteries and proton exchange membrane fuel cells are high in cost; the lithium battery has the problems of safety and sharp reduction of low-temperature discharge performance; the problems of positive material loss and short service life of the magnesium-silver halide seawater battery are still not solved; aluminum-oxygen semi-fuel cells are in the critical phase of electrolyte management systems, oxygen storage and supply systems, hydrogen management systems, and the like.
Compared with the prior art, the seawater dissolved oxygen battery has higher specific energy and lower cost, and the problem that the deep sea power supply battery needs to be provided with a thick pressure-resistant shell is well solved by taking seawater as an electrolyte. Meanwhile, the seawater dissolved oxygen battery is a novel high-specific-energy battery, has the energy density (2900-3000 Wh/kg) higher than that of the traditional battery theoretically, actually obtains a very high energy density result (about 350 Wh/kg), and has the advantages of moderate price, safety, reliability, no need of maintenance, long storage life, good low-temperature performance and the like.
At present, the cathode materials of the seawater batteries which are put into use mainly comprise AgCl, AgO, CuCl and the like, although the activity is high, the electrodes are consumable electrode materials and have relatively short service life, for example, the seawater batteries for marine life-saving lamps developed by Danyang ocean vessel equipment company have the service life of only about 8 hours. In addition, some small-power seawater batteries mainly use graphite, copper, stainless steel and the like as cathodes, however, in the marine environment, the concentration of dissolved oxygen is reduced along with the increase of the depth, the activity of conventional materials is poor, and the enrichment capacity and the reduction efficiency of the dissolved oxygen are low. With the rapid development of marine equipment, the battery cannot meet the long-term operation of the marine equipment, particularly the ultra-long period stable operation of deep-sea instruments and equipment.
Disclosure of Invention
The technical task of the invention is to solve the problems of low oxygen reduction efficiency, poor long-term operation stability and the like of the cathode material of the conventional seawater dissolved oxygen battery, and the invention provides a composite electrode material with a three-dimensional carbon fiber-based Fe @ C-N multilayer coating structure, which has high stability and high catalytic activity, can effectively improve the discharge efficiency of the seawater dissolved oxygen battery, and prolongs the discharge time of the battery. The material is simple in preparation method, low in cost and stable in discharge performance, can be produced in large scale, and can realize super-long-period operation with a seawater battery built by aluminum alloy materials.
The technical principle of the invention is as follows:
the composite material with the multilayer coating structure and high stability and catalytic activity is prepared by combining a convenient chemical deposition method and a high-temperature vacuum treatment method, has the advantages of low price, convenient preparation method, large specific surface area, high oxygen reduction catalytic activity, good stability and the like, and can improve the long-term stability of the seawater dissolved oxygen battery and improve the energy output of the seawater dissolved oxygen battery.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a preparation method of a three-dimensional carbon fiber based multi-layer coating structure composite material of a seawater dissolved oxygen battery, which comprises the following steps:
1) placing the processed carbon fiber matrix with the three-dimensional spiral structure in a high-temperature environment for heat treatment to remove organic impurities on the surface;
2) carrying out ultrasonic cleaning and etching on the carbon fiber matrix with the three-dimensional spiral structure in the step 1) by adopting a hydrochloric acid solution with a certain concentration, and further removing surface inert substances;
3) repeatedly ultrasonically cleaning the carbon fiber substrate in the step 2) by adopting absolute ethyl alcohol, acetone and ultrapure water, removing floating ash and residual acid liquor on the surface, and uniformly spreading carbon fiber tows;
4) preparing ferric nitrate solution, wherein the main components comprise ferric nitrate, sodium sulfate and the like, and adjusting the pH value of the ferric nitrate solution by hydrochloric acid;
5) placing the carbon fiber matrix in the step 3) into a high-temperature closed reactor containing the ferric nitrate solution in the step 4), and carrying out chemical growth reaction for a period of time;
6) cleaning the carbon fiber-FeOOH composite material obtained in the step 5) by using ultrapure water, acetone, absolute ethyl alcohol and the like to remove the FeOOH component and residual liquid which are poorly combined;
7) placing the carbon fiber-FeOOH composite material in the step 6) in a forced air drying oven, and drying at a certain temperature for later use;
8) preparing a pyrrole reaction solution, wherein the components mainly comprise sodium dodecyl sulfate, pyrrole, hydrochloric acid, ammonium persulfate and the like;
9) putting the carbon fiber-FeOOH composite material in the step 7) into the solution prepared in the step 8), and carrying out polypyrrole polymerization growth reaction at a certain temperature to obtain a carbon fiber-FeOOH @ PPy composite material;
10) repeatedly cleaning the carbon fiber-FeOOH @ PPy composite material obtained in the step 9) by using solvents such as absolute ethyl alcohol, ultrapure water and the like to remove residual liquid;
11) placing the composite material obtained in the step 10) in a forced air drying oven, and drying at a certain temperature;
12) and (3) placing the carbon fiber-FeOOH @ PPy composite material obtained in the step (11) into a high-temperature tube furnace, and performing high-temperature vacuum carbonization treatment at a certain temperature to obtain the carbon fiber-Fe @ C-N composite material.
The three-dimensional carbon fiber-Fe @ C-N composite material with the multilayer coating structure, which is prepared by the invention, has the advantages of larger specific surface area, higher discharge potential and good electrocatalytic oxygen reduction performance.
In order to further realize the aim of the invention, the specification of the carbon fiber in the step 1) is 12-24 k, and the cutting length is 3-10 cm;
the high-temperature heat treatment in the step 1) is carried out at 500-700 ℃, and the high-temperature heat treatment time is 1-3 h.
In order to further realize the aim of the invention, the concentration of the hydrochloric acid solution in the step 2) is in the range of 2-10 mol/L, and the ultrasonic etching time is 10-60 min;
the ultrasonic treatment time of the ultrapure water, the acetone, the absolute ethyl alcohol and the like in the step 3) is respectively 30-120 min, 10-30 min and 10-30 min.
In order to further achieve the aim of the invention, the concentration ranges of the components such as ferric nitrate, sodium sulfate and hydrochloric acid in the ferric nitrate solution in the step 4) are respectively 10-20 g/L, 4-10 g/L and 3-7 g/L;
the pH range of the ferric nitrate solution in the step 4) is 3.5-5.5.
In order to further realize the purpose of the invention, the volume range of the ferric nitrate solution in the step 5) is 60-200 mL;
the reaction temperature in the step 5) ranges from 100 ℃ to 150 ℃, and the reaction time ranges from 3h to 8 h.
In order to further achieve the object of the present invention, the number of times of the repeated cleaning of ultrapure water, acetone, absolute ethyl alcohol, etc. in the step 6) is 1 to 5.
In order to further realize the aim of the invention, the drying temperature in the step 7) is in the range of 60-120 ℃, and the drying time is in the range of 12-36 h.
In order to further achieve the purpose of the invention, the concentrations of the reagents such as sodium dodecyl sulfate, pyrrole, ammonium persulfate and the like in the pyrrole reaction solution in the step 8) are respectively 0.05-0.5 g/L, 5-20 g/L and 0.1-0.2 g/L.
In order to further realize the aim of the invention, the solution preparation temperature in the step 8) ranges from 0 ℃ to 10 ℃, the pH value ranges from 0 to 2, and the magnetic stirring rotating speed ranges from 600 rpm/min to 1200 rpm/min.
In order to further realize the aim of the invention, the volume range of the solution in the step 9) is 60-200 mL, the reaction temperature range is 0-10 ℃, the reaction time range is 1-4 h, and the magnetic stirring rotating speed range is 600-1200 rpm/min;
the cleaning times of the absolute ethyl alcohol, the ultrapure water and the like in the step 10) are 2-5 times.
In order to further realize the aim of the invention, the drying temperature in the step 11) is in the range of 60-120 ℃, and the drying time is in the range of 12-36 h;
the temperature range of the high-temperature carbonization treatment in the step 12) is 500-800 ℃, the heating rate is 1-8 ℃/min, and the reaction time is 1-4 h.
Compared with the prior art, the preparation method of the three-dimensional carbon fiber based multi-layer coating structure composite material of the seawater dissolved oxygen battery has the advantages that,
1. the preparation method of the three-dimensional carbon fiber-based Fe @ C-N provided by the invention is simple to operate, low in equipment requirement and high in reproducibility, and can be used for mass production, and the surface of the obtained three-dimensional carbon fiber-Fe @ C-N composite material is of a multi-layer coating structure, so that the structural stability of an electrode material is facilitated;
2. the three-dimensional cladding structure composite electrode material provided by the invention has high electrocatalytic oxygen reduction activity and excellent discharge stability, and can be used for building a seawater dissolved oxygen battery with active metals (such as magnesium alloy, aluminum alloy and the like), has high energy density, and can provide long-period stable power supply for underwater low-power equipment;
3. the three-dimensional cladding structure composite electrode material provided by the invention has wide application, not only can be used as a cathode of a seawater dissolved oxygen battery, but also can be used as an electrode material of a microbial fuel cell, a super capacitor and the like.
Drawings
FIG. 1 is an SEM image of a carbon fiber-Fe @ C-N composite material.
FIG. 2 shows the open circuit potential results of the carbon fiber-Fe @ C-N composite.
FIG. 3 is a constant current discharge curve of the carbon fiber-Fe @ C-N composite material.
FIG. 4 is a power density curve of a carbon fiber-Fe @ C-N composite electrode and a national standard high negative potential aluminum anode seawater battery.
Detailed Description
The following will explain in detail the preparation method of the three-dimensional carbon fiber based multi-layered coating structure composite material of the seawater dissolved oxygen battery in combination with the attached drawings 1-4.
Example one
The invention relates to a preparation method of a three-dimensional carbon fiber based multi-layer coating structure composite material of a seawater dissolved oxygen battery, which comprises the following steps:
1) placing the processed carbon fiber matrix with the three-dimensional spiral structure in a high-temperature environment for heat treatment to remove organic impurities on the surface; wherein the specification of the carbon fiber is 12k, the cutting length is 3cm, the high-temperature heat treatment is 500 ℃, and the high-temperature heat treatment time is 1 h;
2) carrying out ultrasonic cleaning and etching on the carbon fiber substrate with the three-dimensional spiral structure in the step 1) by adopting 2mol/L hydrochloric acid solution, wherein the ultrasonic etching time is 10 min, and further removing surface inert substances;
3) repeatedly ultrasonically cleaning the carbon fiber substrate in the step 2) by adopting absolute ethyl alcohol, acetone and ultrapure water, removing floating ash and residual acid liquor on the surface, and uniformly spreading the carbon fiber tows, wherein the ultrasonic treatment time of the ultrapure water, the acetone, the absolute ethyl alcohol and the like is respectively 30 min, 10 min and 10 min;
4) preparing ferric nitrate solution, wherein the main components comprise ferric nitrate, sodium sulfate and the like, and adjusting the pH value of the ferric nitrate solution by hydrochloric acid; the concentrations of ferric nitrate, sodium sulfate, hydrochloric acid and other components in the ferric nitrate solution are respectively 10 g/L, 4 g/L and 3g/L, and the pH value of the ferric nitrate solution is 3.5;
5) placing the carbon fiber matrix in the step 3) into a high-temperature closed reactor containing the ferric nitrate solution in the step 4), and carrying out chemical growth reaction for a period of time; the volume of the ferric nitrate solution is 60 mL, the reaction temperature is 100 ℃, and the reaction time is 3 h;
6) cleaning the carbon fiber-FeOOH composite material obtained in the step 5) by using ultrapure water, acetone, absolute ethyl alcohol and the like to remove the FeOOH component and residual liquid which are poorly combined; the number of times of repeated cleaning with ultrapure water, acetone, absolute ethyl alcohol and the like is 1;
7) placing the carbon fiber-FeOOH composite material in the step 6) in a forced air drying oven, and drying at a certain temperature for later use, wherein the drying temperature is 60 ℃ and the drying time is 12 h;
8) preparing a pyrrole reaction solution, wherein the components mainly comprise sodium dodecyl sulfate, pyrrole, hydrochloric acid, ammonium persulfate and the like, and the concentrations of reagents such as sodium dodecyl sulfate, pyrrole, ammonium persulfate and the like in the pyrrole reaction solution are respectively 0.05 g/L, 5g/L and 0.1 g/L; wherein the solution preparation temperature is 0 ℃, the pH value is 0, and the magnetic stirring rotating speed is 600 rpm/min;
9) putting the carbon fiber-FeOOH composite material in the step 7) into the solution prepared in the step 8), wherein the volume of the solution is 60 mL, the reaction temperature is 0 ℃, the reaction time is 1h, and the magnetic stirring speed is 600 rpm/min, so that polypyrrole polymerization growth reaction is carried out, and the carbon fiber-FeOOH @ PPy composite material is obtained;
10) repeatedly cleaning the carbon fiber-FeOOH @ PPy composite material obtained in the step 9) by using solvents such as absolute ethyl alcohol and ultrapure water, and removing residual liquid, wherein the cleaning times of the absolute ethyl alcohol, the ultrapure water and the like are 2 times;
11) placing the composite material obtained in the step 10) in a forced air drying oven, and drying at a certain temperature for 12 hours at 60 ℃;
12) and (2) placing the carbon fiber-FeOOH @ PPy composite material obtained in the step 11) in a high-temperature tube furnace, and performing high-temperature vacuum carbonization treatment at a certain temperature to obtain the carbon fiber-Fe @ C-N composite material, wherein the high-temperature carbonization treatment temperature is 500 ℃, the temperature rise rate is 1 ℃/min, and the reaction time is 1 h.
Example two
The invention relates to a preparation method of a three-dimensional carbon fiber based multi-layer coating structure composite material of a seawater dissolved oxygen battery, which comprises the following steps:
1) placing the processed carbon fiber matrix with the three-dimensional spiral structure in a high-temperature environment for heat treatment to remove organic impurities on the surface; wherein the specification of the carbon fiber is 24k, the cutting length is 10cm, the high-temperature heat treatment is carried out at 700 ℃, and the high-temperature heat treatment time is 3 h;
2) carrying out ultrasonic cleaning and etching on the carbon fiber substrate with the three-dimensional spiral structure in the step 1) by adopting 10 mol/L hydrochloric acid solution, wherein the ultrasonic etching time is 60 min, and further removing surface inert substances;
3) repeatedly ultrasonically cleaning the carbon fiber substrate in the step 2) by adopting absolute ethyl alcohol, acetone and ultrapure water, removing floating ash and residual acid liquor on the surface, and uniformly spreading the carbon fiber tows at the same time, wherein the ultrasonic treatment time of the ultrapure water, the acetone, the absolute ethyl alcohol and the like is respectively 120 min, 30 min and 30 min;
4) preparing ferric nitrate solution, wherein the main components comprise ferric nitrate, sodium sulfate and the like, and adjusting the pH value of the ferric nitrate solution by hydrochloric acid; the concentrations of ferric nitrate, sodium sulfate, hydrochloric acid and other components in the ferric nitrate solution are respectively 20 g/L, 10 g/L and 7 g/L, and the pH value of the ferric nitrate solution is 5.5;
5) placing the carbon fiber matrix in the step 3) into a high-temperature closed reactor containing the ferric nitrate solution in the step 4), and carrying out chemical growth reaction for a period of time; the volume of the ferric nitrate solution is 200 mL, the reaction temperature is 150 ℃, and the reaction time is 8 h;
6) cleaning the carbon fiber-FeOOH composite material obtained in the step 5) by using ultrapure water, acetone, absolute ethyl alcohol and the like to remove the FeOOH component and residual liquid which are poorly combined; the number of times of repeated cleaning with ultrapure water, acetone, absolute ethyl alcohol and the like is 5;
7) placing the carbon fiber-FeOOH composite material in the step 6) in a forced air drying oven, and drying at a certain temperature for later use, wherein the drying temperature is 120 ℃, and the drying time is 36 h;
8) preparing a pyrrole reaction solution, wherein the components mainly comprise sodium dodecyl sulfate, pyrrole, hydrochloric acid, ammonium persulfate and the like, and the concentrations of reagents such as sodium dodecyl sulfate, pyrrole, ammonium persulfate and the like in the pyrrole reaction solution are respectively 0.5 g/L, 20 g/L and 0.2 g/L; wherein the solution preparation temperature is 10 ℃, the pH value is 2, and the magnetic stirring rotating speed is 1200 rpm/min;
9) putting the carbon fiber-FeOOH composite material in the step 7) into the solution prepared in the step 8), wherein the volume of the solution is 200 mL, the reaction temperature is 10 ℃, the reaction time is 4h, and the magnetic stirring speed is 1200 rpm/min, so that polypyrrole polymerization growth reaction is carried out, and the carbon fiber-FeOOH @ PPy composite material is obtained;
10) repeatedly cleaning the carbon fiber-FeOOH @ PPy composite material obtained in the step 9) by using solvents such as absolute ethyl alcohol and ultrapure water, and removing residual liquid, wherein the cleaning times of the absolute ethyl alcohol and the ultrapure water are 5 times;
11) placing the composite material obtained in the step 10) in a forced air drying oven, and drying at a certain temperature of 120 ℃ for 36 h;
12) and (2) placing the carbon fiber-FeOOH @ PPy composite material obtained in the step 11) in a high-temperature tube furnace, and performing high-temperature vacuum carbonization treatment at a certain temperature to obtain the carbon fiber-Fe @ C-N composite material, wherein the high-temperature carbonization treatment temperature is 800 ℃, the temperature rise rate is 8 ℃/min, and the reaction time is 4 h.
EXAMPLE III
The invention relates to a preparation method of a three-dimensional carbon fiber based multi-layer coating structure composite material of a seawater dissolved oxygen battery, which comprises the following steps:
1) placing the processed carbon fiber matrix with the three-dimensional spiral structure in a high-temperature environment for heat treatment to remove organic impurities on the surface; wherein the specification of the carbon fiber is 18k, the cutting length is 7cm, the high-temperature heat treatment is 600 ℃, and the high-temperature heat treatment time is 2 hours;
2) carrying out ultrasonic cleaning and etching on the carbon fiber substrate with the three-dimensional spiral structure in the step 1) by adopting 6 mol/L hydrochloric acid solution, wherein the ultrasonic etching time is 30 min, and further removing surface inert substances;
3) repeatedly ultrasonically cleaning the carbon fiber substrate in the step 2) by adopting absolute ethyl alcohol, acetone and ultrapure water, removing floating ash and residual acid liquor on the surface, and uniformly spreading the carbon fiber tows, wherein the ultrasonic treatment time of the ultrapure water, the acetone, the absolute ethyl alcohol and the like is respectively 60 min, 20 min and 20 min;
4) preparing ferric nitrate solution, wherein the main components comprise ferric nitrate, sodium sulfate and the like, and adjusting the pH value of the ferric nitrate solution by hydrochloric acid; the concentrations of ferric nitrate, sodium sulfate, hydrochloric acid and other components in the ferric nitrate solution are respectively 15g/L, 6g/L and 5g/L, and the pH value of the ferric nitrate solution is 4.0;
5) placing the carbon fiber matrix in the step 3) into a high-temperature closed reactor containing the ferric nitrate solution in the step 4), and carrying out chemical growth reaction for a period of time; the volume of the ferric nitrate solution is 100 mL, the reaction temperature is 120 ℃, and the reaction time is 6 h;
6) cleaning the carbon fiber-FeOOH composite material obtained in the step 5) by using ultrapure water, acetone, absolute ethyl alcohol and the like to remove the FeOOH component and residual liquid which are poorly combined; the number of times of repeated cleaning with ultrapure water, acetone, absolute ethyl alcohol, etc. is 3;
7) placing the carbon fiber-FeOOH composite material in the step 6) in a forced air drying oven, and drying at a certain temperature for later use, wherein the drying temperature is 100 ℃, and the drying time is 24 hours;
8) preparing a pyrrole reaction solution, wherein the components mainly comprise sodium dodecyl sulfate, pyrrole, hydrochloric acid, ammonium persulfate and the like, and the concentrations of reagents such as sodium dodecyl sulfate, pyrrole, ammonium persulfate and the like in the pyrrole reaction solution are respectively 0.1 g/L, 10 g/L and 0.15 g/L; wherein the solution preparation temperature is 5 ℃, the pH value is 1, and the magnetic stirring rotating speed is 1000 rpm/min;
9) putting the carbon fiber-FeOOH composite material in the step 7) into the solution prepared in the step 8), wherein the volume of the solution is 100 mL, the reaction temperature is 5 ℃, the reaction time is 2h, and the magnetic stirring rotating speed is 800 rpm/min, so that polypyrrole polymerization growth reaction is carried out, and the carbon fiber-FeOOH @ PPy composite material is obtained;
10) repeatedly cleaning the carbon fiber-FeOOH @ PPy composite material obtained in the step 9) by using solvents such as absolute ethyl alcohol and ultrapure water, and removing residual liquid, wherein the cleaning times of the absolute ethyl alcohol, the ultrapure water and the like are 3 times;
11) placing the composite material obtained in the step 10) in a forced air drying oven, and drying at a certain temperature of 90 ℃ for 24 hours;
12) and (2) placing the carbon fiber-FeOOH @ PPy composite material obtained in the step 11) into a high-temperature tube furnace, and performing high-temperature vacuum carbonization treatment at a certain temperature to obtain the carbon fiber-Fe @ C-N composite material, wherein the high-temperature carbonization treatment temperature is 600 ℃, the temperature rise rate is 4 ℃/min, and the reaction time is 3 h.
TABLE 1 example EDS results for a carbon fiber-Fe @ C-N composite
Element(s) | C | O | N | Fe |
Weight percent of | 17.16% | 16.44% | 11.32% | 55.08% |
Mole percent of | 33.65% | 24.18% | 19.03% | 23.14% |
FIGS. 1-4 are SEM images of a carbon fiber-Fe @ C-N composite material, open-circuit potential results of the carbon fiber-Fe @ C-N composite material, constant-current discharge curves of the carbon fiber-Fe @ C-N composite material, and power density curves of a carbon fiber-Fe @ C-N composite electrode and a national standard high negative potential aluminum anode seawater battery in one embodiment.
The three-dimensional carbon fiber-Fe @ C-N composite material with the multilayer coating structure, which is prepared by the invention, has the advantages of larger specific surface area, higher discharge potential and good electrocatalytic oxygen reduction performance.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A preparation method of a three-dimensional carbon fiber based multi-layer coating structure composite material of a seawater dissolved oxygen battery is characterized by comprising the following steps:
1) placing the processed carbon fiber matrix with the three-dimensional spiral structure in a high-temperature environment for heat treatment to remove organic impurities on the surface;
2) carrying out ultrasonic cleaning and etching on the carbon fiber matrix with the three-dimensional spiral structure in the step 1) by adopting a hydrochloric acid solution with a certain concentration, and further removing surface inert substances;
3) repeatedly ultrasonically cleaning the carbon fiber substrate in the step 2) by adopting absolute ethyl alcohol, acetone and ultrapure water, removing floating ash and residual acid liquor on the surface, and uniformly spreading carbon fiber tows;
4) preparing ferric nitrate solution, wherein the main components comprise ferric nitrate and sodium sulfate, and adjusting the pH value of the ferric nitrate solution by hydrochloric acid;
5) placing the carbon fiber matrix in the step 3) into a high-temperature closed reactor containing the ferric nitrate solution in the step 4), and carrying out chemical growth reaction for a period of time;
6) cleaning the carbon fiber-FeOOH composite material obtained in the step 5) by using ultrapure water, acetone and absolute ethyl alcohol to remove the FeOOH component and residual liquid which are poorly combined;
7) placing the carbon fiber-FeOOH composite material in the step 6) in a forced air drying oven, and drying at a certain temperature for later use;
8) preparing a pyrrole reaction solution, wherein the components mainly comprise sodium dodecyl sulfate, pyrrole, hydrochloric acid and ammonium persulfate;
9) putting the carbon fiber-FeOOH composite material in the step 7) into the solution prepared in the step 8), and carrying out polypyrrole polymerization growth reaction at a certain temperature to obtain a carbon fiber-FeOOH @ PPy composite material;
10) repeatedly cleaning the carbon fiber-FeOOH @ PPy composite material obtained in the step 9) through absolute ethyl alcohol and an ultra-pure water solvent to remove residual liquid;
11) placing the composite material obtained in the step 10) in a forced air drying oven, and drying at a certain temperature;
12) and (3) placing the carbon fiber-FeOOH @ PPy composite material obtained in the step (11) into a high-temperature tube furnace, and performing high-temperature vacuum carbonization treatment at a certain temperature to obtain the carbon fiber-Fe @ C-N composite material.
2. The preparation method of the three-dimensional carbon fiber based multilayer coating structure composite material of the seawater dissolved oxygen battery according to claim 1, wherein the carbon fiber in the step 1) is 12-24 k in specification, and the cutting length is 3-10 cm.
3. The preparation method of the three-dimensional carbon fiber based multilayer coating structure composite material of the seawater dissolved oxygen battery as claimed in claim 1, wherein the high temperature heat treatment in step 1) is between 500 and 700 ℃, and the high temperature heat treatment time is between 1 and 3 hours;
in the step 2), the concentration of the hydrochloric acid solution is in the range of 2-10 mol/L, and the ultrasonic etching time is 10-60 min;
the ultrasonic treatment time of the ultrapure water, the acetone and the absolute ethyl alcohol in the step 3) is respectively 30-120 min, 10-30 min and 10-30 min.
4. The preparation method of the three-dimensional carbon fiber based multilayer coating structure composite material of the seawater dissolved oxygen battery as claimed in claim 1, wherein the concentration ranges of the ferric nitrate, the sodium sulfate and the hydrochloric acid in the ferric nitrate solution in the step 4) are respectively 10-20 g/L, 4-10 g/L and 3-7 g/L;
the pH range of the ferric nitrate solution in the step 4) is 3.5-5.5.
5. The method for preparing the three-dimensional carbon fiber based multilayer coating structure composite material of the seawater dissolved oxygen battery as claimed in claim 1, wherein the volume range of the ferric nitrate solution in the step 5) is 60-200 mL;
the reaction temperature in the step 5) ranges from 100 ℃ to 150 ℃, and the reaction time ranges from 3h to 8 h.
6. The method for preparing the three-dimensional carbon fiber based multilayer coating structure composite material of the seawater dissolved oxygen battery as claimed in claim 1, wherein the number of times of repeatedly cleaning the ultrapure water, the acetone and the absolute ethyl alcohol in the step 6) is 1-5.
7. The preparation method of the three-dimensional carbon fiber based multilayer coating structure composite material of the seawater dissolved oxygen battery as claimed in claim 1, wherein the drying temperature in the step 7) is 60-120 ℃, and the drying time is 12-36 h.
8. The method for preparing the three-dimensional carbon fiber based multilayer coating structure composite material of the seawater dissolved oxygen battery according to claim 1, wherein the concentrations of the reagents of sodium dodecyl sulfate, pyrrole and ammonium persulfate in the pyrrole reaction solution in the step 8) are respectively 0.05-0.5 g/L, 5-20 g/L and 0.1-0.2 g/L;
the solution preparation temperature in the step 8) ranges from 0 ℃ to 10 ℃, the pH value ranges from 0 to 2, and the magnetic stirring rotating speed ranges from 600 rpm/min to 1200 rpm/min.
9. The preparation method of the three-dimensional carbon fiber based multilayer coating structure composite material of the seawater dissolved oxygen battery according to claim 1, wherein the volume of the solution in the step 9) ranges from 60 mL to 200 mL, the reaction temperature ranges from 0 ℃ to 10 ℃, the reaction time ranges from 1h to 4h, and the magnetic stirring rotation speed ranges from 600 rpm/min to 1200 rpm/min;
the cleaning times of the absolute ethyl alcohol and the ultrapure water in the step 10) are 2-5 times.
10. The preparation method of the three-dimensional carbon fiber based multilayer coating structure composite material of the seawater dissolved oxygen battery as claimed in claim 1, wherein the drying temperature in the step 11) is 60-120 ℃, and the drying time is 12-36 h;
the temperature range of the high-temperature carbonization treatment in the step 12) is 500-800 ℃, the heating rate is 1-8 ℃/min, and the reaction time is 1-4 h.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110673038.5A CN113629257A (en) | 2021-06-17 | 2021-06-17 | Preparation method of three-dimensional carbon fiber based multi-layer coating structure composite material of seawater dissolved oxygen battery |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110673038.5A CN113629257A (en) | 2021-06-17 | 2021-06-17 | Preparation method of three-dimensional carbon fiber based multi-layer coating structure composite material of seawater dissolved oxygen battery |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113629257A true CN113629257A (en) | 2021-11-09 |
Family
ID=78378162
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110673038.5A Pending CN113629257A (en) | 2021-06-17 | 2021-06-17 | Preparation method of three-dimensional carbon fiber based multi-layer coating structure composite material of seawater dissolved oxygen battery |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113629257A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114804509A (en) * | 2022-03-30 | 2022-07-29 | 河北大学 | System and method for repairing high nitrate nitrogen underground water by using secondary effluent |
-
2021
- 2021-06-17 CN CN202110673038.5A patent/CN113629257A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114804509A (en) * | 2022-03-30 | 2022-07-29 | 河北大学 | System and method for repairing high nitrate nitrogen underground water by using secondary effluent |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107342421B (en) | High-content pyridine nitrogen-doped porous carbon negative electrode material, and preparation method and application thereof | |
CN109546163B (en) | Modification method of graphite felt electrode for organic flow battery | |
CN101626083B (en) | Method for preparing proton exchange membrane fuel cell electrode with high catalyst utilization ratio | |
CN103137943B (en) | Positive electrode used for seawater dissolved oxygen battery and seawater dissolved oxygen battery employing same | |
CN108432021A (en) | Three electrode list liquid stream zinc-air battery of level with floating cathode | |
CN102903921A (en) | Aqueous battery using carbon fluoride as anode | |
CN212967770U (en) | Underwater microbial fuel cell generating device | |
CN108615959A (en) | A kind of hydrophilic cathode of dissolved oxygen seawater battery and its preparation and application | |
CN108365172A (en) | A kind of lithium an- ode material and its preparation method and application of natural polymers protection | |
WO2020078897A1 (en) | Carbon electrode for dichromate redox flow batteries | |
CN113629257A (en) | Preparation method of three-dimensional carbon fiber based multi-layer coating structure composite material of seawater dissolved oxygen battery | |
CN109326798A (en) | A kind of preparation method and application for lithium anode protective layer | |
CN109904477B (en) | Emergency metal seawater battery for sea surface | |
CN106654163A (en) | Preparation method of cathode of seawater dissolved oxygen battery | |
CN108172947B (en) | Double-function electrode and preparation and application thereof | |
Kube et al. | Influence of organic additives for zinc-air batteries on cathode stability and performance | |
CN109786861B (en) | Hybrid electrochemical energy storage device | |
US20130075270A1 (en) | Method for coating metallic interconnect of solid fuel cell | |
Wang et al. | Performance improvement of underwater Mg-oxygen battery with parameter optimization | |
CN113067059B (en) | Preparation method of electrolyte for magnesium air battery | |
CN110474023A (en) | A kind of fibrous nickel bismuth battery and preparation method thereof | |
CN110350146A (en) | A kind of porous antimony electrode of modified 3 D, preparation method and application | |
CN107482284B (en) | Lithium oxygen battery | |
CN115881915A (en) | Large-scale preparation method for in-situ construction of zinc cathode metal composite protective layer by ultrafast microwave technology and application thereof | |
CN115010941A (en) | Preparation method and application of ionic covalent organic framework nanosheet protective layer through electrodeposition |
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 |