CN110931266A - 3D flowering rod-shaped nickel sulfide/wood electrode material and preparation method and application thereof - Google Patents
3D flowering rod-shaped nickel sulfide/wood electrode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN110931266A CN110931266A CN201911102278.9A CN201911102278A CN110931266A CN 110931266 A CN110931266 A CN 110931266A CN 201911102278 A CN201911102278 A CN 201911102278A CN 110931266 A CN110931266 A CN 110931266A
- Authority
- CN
- China
- Prior art keywords
- wood
- flowering
- rod
- electrode material
- nickel sulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/11—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Abstract
The invention provides a 3D flowering rod-shaped nickel sulfide/wood electrode material and a preparation method and application thereof, wherein the method comprises the following steps of 1, wherein the molar concentration ratio is (4-7): (3-6) filling the mixed solution of nickel chloride and thiourea in delignified wood to obtain delignified wood containing the mixed solution; step 2, removing water in the delignified wood containing the mixed solution to obtain dry filled wood; step 3, firstly, preserving heat of the dried filling wood at 180-360 ℃ for 3-6 h in an oxygen environment, and then preserving heat at 700-900 ℃ for 2-5 h in an oxygen-free environment to obtain a 3D flowering rod-shaped nickel sulfide/wood electrode material; the conductivity, current density, power density and energy density of the material are improved, and the material has higher power density under the condition of certain energy density.
Description
Technical Field
The invention belongs to the technical field of biomass energy, and particularly relates to a 3D flowering rod-shaped nickel sulfide/wood electrode material and a preparation method and application thereof.
Background
The super capacitor, namely the electrochemical capacitor, is a novel energy storage device between a traditional capacitor and a secondary capacitor, and has higher energy density than the traditional capacitor and higher power density than a secondary battery. In addition, the super capacitor also has the advantages of flexible capacity configuration, easy realization of modular design, long cycle service life, wide working temperature range, environmental friendliness, maintenance-free property and the like, and the characteristics make the super capacitor more suitable for harsh working environment. In recent years, with the development of carbon nanotechnology, the manufacturing cost of the super capacitor is continuously reduced, and the power density and the energy density of the super capacitor are continuously improved, which will further expand and accelerate the application of the super capacitor in the aspect of novel power energy storage. The super capacitor can partially or completely replace the traditional chemical battery for a traction power supply and a starting power supply of a vehicle due to the excellent characteristics of the super capacitor, and has wider application range than the traditional chemical battery. Because of this, research and development of supercapacitors is carried out in various countries of the world without much effort.
In the electrode material of the super capacitor, the carbon-based material is the most used electrode material due to the advantages of porosity, high specific surface area structure, good conductivity, wide pore size distribution and the like. Carbon-based materials store electrical energy using an electric double layer, and it has been once thought that the specific capacitance of a capacitor can be increased by increasing the specific surface area of the carbon-based material. However, through years of research, the specific surface area of the carbon-based material is not the only factor influencing the electrochemical performance of the supercapacitor. The porosity of the carbon-based material and the functional groups adsorbed on the surface of the carbon-based material jointly restrict the utilization rate of the specific surface area of the carbon-based material, wherein the porosity of the carbon-based material directly influences the infiltration condition of the electrolyte on the carbon-based material, and the good infiltration effect is favorable for positive and negative charges stored in the assembled carbon-based material during a performance test to form an electric double layer. Carbon-based materials reported so far are activated carbon, carbon fiber, carbon aerogel, carbon nanotube, graphene and the like, but the preparation process of the carbon-based materials is complex and difficult for large-scale production, such as single-wall and multi-wall carbon nanotube, and in addition, the carbon-based materials have defects, which seriously affect the large-scale application of the supercapacitor material.
Therefore, more and more scientists aim at the biomass material, and the biomass material is more and more concerned by people due to the wide existence of the biomass material in nature, contains a large amount of carbon elements and has various superior spatial structures which cannot be compared with the biomass material by chemical synthesis, so that a great deal of possibility is provided for the full utilization of people; meanwhile, the biomass material has the characteristics of perfect biological cycle, has zero pollution to the environment, can be regenerated in hundreds of percent, and is also the dust of other artificially synthesized materials. The prepared functional material has wide application in the aspects of intelligent materials, biomedicine, light textile industry and the like, but the current density and the energy density of the existing biomass energy storage material are low, so that the biomass material has long charging time, long discharging time and limited energy storage.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a 3D flowering rod-shaped nickel sulfide/wood electrode material, a preparation method and application thereof, the process is simple, safe and pollution-free, and the 3D flowering rod-shaped structure provides effective pore channels for the infiltration of electrolyte and the storage and transmission of electrons, so that the current density, the energy density and the charge/discharge cycle stability of the material are improved.
The invention is realized by the following technical scheme:
a preparation method of a 3D flowering rod-shaped nickel sulfide/wood electrode material comprises the following steps,
step 1, mixing the following components in a molar concentration ratio of (4-7): (3-6) filling the mixed solution of nickel chloride and thiourea in delignified wood to obtain delignified wood containing the mixed solution;
step 2, removing water in the delignified wood containing the mixed solution to obtain dry filled wood;
and 3, firstly, preserving heat of the dried filling wood at 180-360 ℃ for 3-6 h in an oxygen environment, and then preserving heat at 700-900 ℃ for 2-5 h in an oxygen-free environment to obtain the 3D flowering rod-shaped nickel sulfide/wood electrode material.
Preferably, in step 1, said delignified wood is obtained by,
step 1a, soaking wood in a mixed aqueous solution of sodium chlorite and glacial acetic acid, and taking out the wood after the wood is kept for 3-12 hours at the temperature of 70-85 ℃;
and step 1b, freezing the wood obtained in the step 1a at the temperature of below-5 ℃ for 6-12 h, and then carrying out freeze drying at the temperature of below-5 ℃ for 5-12 h to obtain delignified wood.
Further, in the step 1a, the wood is in a cuboid shape, the length of the wood is 2-6 cm, the width of the wood is 1-3 cm, and the thickness of the wood is 2-5 mm;
in the mixed solution of sodium chlorite and glacial acetic acid, the ratio of the sodium chlorite to the glacial acetic acid to the deionized water is (0.3-0.5) g: (0.5-2) ml: (10-50) ml.
And further, in the step 1a, soaking the wood in a mixed solution of sodium chlorite and glacial acetic acid at the rotating speed of 50-300 rpm.
Preferably, in the step 1, the mixed solution of the nickel chloride and the thiourea is blown into the delignified wood by adopting a vacuum pumping and nitrogen blowing method, so as to obtain the delignified wood containing the mixed solution.
Preferably, in step 2, a dried filled wood is obtained as follows,
and (3) freezing the delignified wood containing the mixed solution at the temperature of below-5 ℃ for 6-12 h, and then freezing and drying the delignified wood at the temperature of below-5 ℃ for 5-12 h to obtain the dried filled wood.
Preferably, in the step 3, the temperature of the dried filling wood is raised to 180-360 ℃ at the rate of 3-10 ℃/min, and then the temperature is raised to 700-900 ℃ at the rate of 3-10 ℃/min.
The 3D flowering rod-shaped nickel sulfide/wood electrode material is obtained by the preparation method of the 3D flowering rod-shaped nickel sulfide/wood electrode material.
A capacitor comprising the 3D flowering rod-shaped nickel sulfide/wood electrode material.
An electronic device comprising the capacitor drive.
Compared with the prior art, the invention has the following beneficial technical effects:
the preparation method of the 3D flowering rod-shaped nickel sulfide/wood electrode material comprises the following steps of: (3-6) filling the mixed solution of nickel chloride and thiourea in delignified wood, removing water, performing programmed high-temperature treatment, wherein nickel sulfide can be formed on the wood by the nickel chloride and thiourea, on one hand, the delignified wood provides an effective pore structure for the growth of the nickel sulfide, and a large amount of high-purity carbon is introduced to construct a good conductive network for the material, on the other hand, because the programmed temperature rise enables the nickel sulfide to grow into linear crystals firstly, the nickel sulfide is continuously wrapped on the linear crystals by the platelets along with the temperature rise, in the method, the platelets continue to grow, the general temperature is different, the generated shapes are different, and the platelets are sequentially treated at 180-360 ℃ and 700-900 ℃ to form the nickel sulfide/wood composite material with the 3D flowering rod shape, so that the conductivity, the current density, the power density and the energy density of the material are improved, and the material has higher power density under the condition of certain energy density; according to the invention, the control of the appearance and thickness of the vulcanized layer is realized by controlling the concentration of the mixed aqueous solution of nickel chloride and thiourea, so that the large-scale preparation of the supercapacitor material is possible on the premise of not influencing the performance of the vulcanized layer.
Furthermore, the wood is soaked in the mixed aqueous solution of sodium chlorite and glacial acetic acid, and then is frozen and then is freeze-dried, so that the lignin is completely removed, and the delignified wood containing a large number of pore passages is obtained.
Furthermore, the time required for delignification can be reduced by controlling the shape and size of the wood and the ratio of sodium chlorite to glacial acetic acid.
In the 3D flowering rod-shaped nickel sulfide/wood electrode material, the 3D flowering rod-shaped nickel sulfide material provides a large amount of specific surface area for storing charges, and is combined with pure carbon wood with an array porous structure, so that the charge transmission and storage are accelerated, and meanwhile, large current density and energy density are provided for the material; due to the introduction of a large amount of biomass energy, a new thought and an example are provided for the development of novel energy materials.
Drawings
Fig. 1a is a scanning electron microscope image of lignin-removed wood provided in example 1 of the present invention at 200 μm.
FIG. 1b is a scanning electron microscope image of the lignin-removed wood provided in example 1 of the present invention at 50 μm.
FIG. 2 is a scanning electron microscope image of a growing 3D flowering rod-shaped nickel sulfide/wood electrode material provided in example 1 of the present invention at 100 μm.
FIG. 3 is a scanning electron microscope image of a growing 3D flowering rod-shaped nickel sulfide/wood electrode material provided in example 1 of the present invention at 20 μm.
FIG. 4 is a scanning electron microscope image of a growing 3D flowering rod-shaped nickel sulfide/wood electrode material provided in example 1 of the present invention at 10 μm.
FIG. 5 is a scanning electron microscope image of a growing 3D flowering rod-shaped nickel sulfide/wood electrode material provided in example 1 of the present invention at 5 μm.
FIG. 6 is a graphical representation of voltage-current density curves at a scan rate of 10mv/s for growing 3D flowering rod-shaped nickel sulfide/wood electrode materials and carbonized porous wood, carbonized porous wood @ nickel chloride hexahydrate-thiourea/small volume polymer, carbonized porous wood @ nickel chloride hexahydrate-thiourea/large volume polymer provided in example 1 of the present invention.
Fig. 7 is a graphical representation of time-voltage curves for growing 3D flowering rod-shaped nickel sulfide/wood electrode materials and carbonized porous wood, carbonized porous wood @ nickel chloride hexahydrate-thiourea/low polymer, carbonized porous wood @ nickel chloride hexahydrate-thiourea/high polymer at a charge and discharge rate of 1.5A/g as provided in example 1 of the present invention.
FIG. 8 is a graph of growth 3D flowering rod nickel sulfide/wood electrode material and carbonized porous wood, carbonized porous wood @ nickel chloride hexahydrate-thiourea/small polymer, carbonized porous wood @ nickel chloride hexahydrate-thiourea/large polymer at 100mV s as provided in example 1 of the present invention-1Voltage-current density curve at the scan rate of (a).
Figure 9 is a graphical representation of the time-voltage curves at a charge and discharge rate of 10A/g for a growing 3D flowering rod of nickel sulfide/wood electrode material and carbonized porous wood @ nickel chloride hexahydrate-thiourea/low polymer provided in example 1 of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The method comprises the steps of taking wood widely distributed in nature as a natural carbon source, combining a biomass technology to prepare a supercapacitor electrode material, preparing a 3D flowering rod-shaped nickel sulfide/wood composite material by adopting a chemical vapor deposition (abbreviated as CVD) method, selecting thiourea as a sulfur source and nickel chloride hexahydrate as a nickel source, blowing a nickel chloride hexahydrate and thiourea mixed solution into wood pore channels by a vacuum pumping and nitrogen blowing method, specifically, pumping out gas in the wood pore channels to enable the wood pore channels to be in a negative pressure state, and applying nitrogen pressure, wherein the nickel chloride hexahydrate and thiourea mixed solution around the wood pore channels can enter the wood pore channels along with the pressure; and (3) carrying out high-temperature vulcanization treatment on the nickel chloride hexahydrate by adopting a CVD (chemical vapor deposition) method, so that the flowering rod-shaped nickel sulfide uniformly grows on the pore canal and the surface of the wood to obtain the composite material with the nickel sulfide wood.
At present, almost all crystal growth methods can be used for the synthesis of transition metal chalcogenide compounds, nickel sulfide materials have wide sources, and a large amount of substances can be used during preparation, and high-temperature gas phase synthesis, solid phase synthesis, ion exchange synthesis, organic matter decomposition, electrochemical synthesis or gamma radiation and the like are generally adopted to prepare transition metal sulfides with different shapes, such as rods, petals, needles, spheres, octahedrons and the like, although the components are the same, the surface area space crystal structures of different shapes are different, which influences the properties of the transition metal sulfide, such as strength, toughness, stored charge amount, micro-regularity of the material, and the like, in particular nickel sulfide, the flowering rod-shaped nickel sulfide obtained by the invention grows on wood with a large number of pore channels, so that a good conductive network is constructed for the material, the conductivity of the material is improved, so that the material has higher power density under the condition of high energy density and certain value.
The invention relates to a preparation method of a 3D flowering rod-shaped nickel sulfide/wood electrode material, which comprises the following steps as shown in figure 1,
step 1, preparation of dry delignified wood, also available in the prior art,
firstly, cutting wood into regular shapes, wherein the wood can be in any shape, generally is a cuboid, weighing 0.3-0.5 g of sodium chlorite and 0.5-2 ml of glacial acetic acid with the length of 2-6 cm, the width of 1-3 cm and the thickness of 2-5 mm, putting the weighed sodium chlorite and the weighed glacial acetic acid into a 100ml beaker, dissolving the beaker in 10-50 ml of deionized water, and putting the prepared wood into the beaker;
obtaining delignified wood through 3-12 hours at the rotating speed of 50-300 rpm at 70-85 ℃, putting the delignified wood into a refrigerator, freezing the delignified wood for 6-12 hours below-5 ℃, and freeze-drying the delignified wood for 5-12 hours below-5 ℃ to obtain dried delignified wood, wherein the freezing is firstly used for removing water in the material by using a freeze-drying method, and if the material is naturally dried, the pore channels of the material collapse, the material deforms, and the pore channels are damaged, so that the pore channels cannot be used for filling metal;
step 2, preparing a mixed aqueous solution of nickel chloride hexahydrate and thiourea, wherein the concentrations of the nickel chloride hexahydrate and the thiourea are (4-7) mol/L and (3-6) mol/L in sequence, performing ultrasonic dispersion by using a cell crusher, and blowing the mixed solution of the nickel chloride hexahydrate and the thiourea into the treated wood by adopting a vacuum pumping and nitrogen blowing method;
putting the wood filled with the mixed aqueous solution of the nickel chloride hexahydrate and the thiourea into a refrigerator, freezing the wood for 6-12 hours at the temperature of below-5 ℃, and freeze-drying the wood for 5-12 hours at the temperature of below-5 ℃ to obtain the dried filled wood of the nickel chloride hexahydrate and the thiourea, wherein the crystal water in the wood can be removed by freeze-drying;
step 3, putting the dried wood filled with nickel chloride hexahydrate and thiourea into a tube furnace, introducing air, heating to 180-360 ℃ at the speed of 3-10 ℃/min in an oxygen environment, preserving heat for 3-6 h, then introducing high-purity argon or nitrogen, heating to 700-900 ℃ at the speed of 3-10 ℃/min, preserving heat for 2-5 h again, wherein the heating rate is relatively mild, and the stable generation of 3D flowering rod-shaped nickel sulfide on the wood is facilitated;
and after the procedure is finished, opening the tube furnace when the temperature is reduced to the room temperature, so that the sample is conveniently taken out, and obtaining the 3D flowering rod-shaped nickel sulfide/wood electrode material.
Example 1
The invention relates to a preparation method of a 3D flowering rod-shaped nickel sulfide/wood electrode material, which comprises the following steps,
step 1, firstly, cutting wood into slices with the length of 4cm, the width of 1cm and the thickness of 2mm, weighing 0.4g of sodium chlorite and 1.3ml of glacial acetic acid, putting the weighed slices into a 100ml beaker, dissolving the weighed slices in 25ml of deionized water, and putting the prepared wood into the beaker;
obtaining delignified wood after 12 hours at the temperature of 80 ℃ and the rotating speed of 100rpm, putting the delignified wood into a refrigerator, freezing for 12 hours at the temperature of-5 ℃, and then freezing and drying for 5 hours at the temperature of-5 ℃ to obtain dried delignified wood;
step 2, preparing a mixed aqueous solution with the concentration of nickel chloride hexahydrate and thiourea being 6mol/L, performing ultrasonic dispersion by using a cell crushing instrument, and blowing the mixed solution of the nickel chloride hexahydrate and the thiourea into the treated wood by adopting a vacuumizing and nitrogen blowing method;
putting the wood filled with the mixed aqueous solution of the nickel chloride hexahydrate and the thiourea into a refrigerator again, freezing the wood at the temperature of-5 ℃ for 12 hours, and then freezing and drying the wood at the temperature of-5 ℃ for 5 hours to obtain the dried filled wood of the nickel chloride hexahydrate and the thiourea;
step 3, putting the dried wood filled with the nickel chloride hexahydrate and the thiourea into a tube furnace, introducing air, heating to 260 ℃ at the speed of 5 ℃/min, preserving heat for 6h, introducing high-purity argon, heating to 800 ℃ at the speed of 5 ℃/min, and preserving heat for 6h again;
and (4) after the procedure is finished, opening the tube furnace when the temperature is reduced to the room temperature, and taking out the sample to obtain the 3D flowering rod-shaped nickel sulfide/wood electrode material.
As shown in fig. 1a and 1b, which are only different in magnification, both figures show that the delignified wood contains a large number of 3D pore structures.
As shown in fig. 2, fig. 3, fig. 4 and fig. 5, wherein fig. 2 shows that 3D blossoming rod-shaped three-dimensional nickel sulfide uniformly grows and distributes on the surface of the wood, fig. 3, fig. 4 and fig. 5 show that the petal-shaped growth morphology of nickel sulfide uniformly grows on the wood, and the blossoming rod-shaped nickel sulfide can be clearly seen under high magnification.
A diaphragm is placed between two electrode materials which are both 3D flowering rod-shaped nickel sulfide/wood, a brand new capacitor is assembled, carbonized porous wood @ nickel chloride hexahydrate-thiourea is used for replacing the electrode materials of the 3D flowering rod-shaped nickel sulfide/wood, the carbonized porous wood @ nickel chloride hexahydrate-thiourea/a small amount of polymer and the carbonized porous wood @ nickel chloride hexahydrate-thiourea/a large amount of polymer are assembled into the capacitor in the same mode, and test results are described respectively.
The carbonized porous wood is obtained by directly carbonizing the dried delignified wood obtained in the step 1 according to the process of the step 3, the carbonized porous wood @ nickel chloride hexahydrate is obtained by blowing 6mol/L of nickel chloride hexahydrate into the dried delignified wood obtained in the step 1, then freezing, freeze-drying and carbonizing in the process of the step 1, the carbonized porous wood @ nickel chloride hexahydrate-thiourea/a small amount of polymer and the carbonized porous wood @ nickel chloride hexahydrate-thiourea/a large amount of polymer are prepared only in different adding amounts of the polymer, the polymer is Vitrimer, is a high-molecular cross-linked reticular polymer, and the calculated amount of 0.1-0.3 g of Vitrimer synthesized in each square centimeter area is small and more than 1g of the Vitrimer is large according to the thickness of the material being 3 mm. The carbonized porous wood @ nickel chloride hexahydrate-thiourea/small amount of polymer and the carbonized porous wood @ nickel chloride hexahydrate-thiourea/large amount of polymer are prepared by dripping Virimer on a 3D flowering rod-shaped nickel sulfide/wood electrode material and drying in a 90 ℃ oven for 12h in-situ polymerization, and have the functions of firstly preventing fluffiness and frangibility generated after the material is carbonized, and secondly reducing the expansion effect of the material and prolonging the service life of the material in the charge and discharge processes of the material.
As shown in fig. 6, carbonized porous wood @ nickel chloride hexahydrate-thiourea hexahydrate/small amount of polymer and carbonized porous wood @ nickel chloride hexahydrate-thiourea/large amount of polymer were scanned at a scan rate of 10mv/s under cyclic voltammetry test. The voltage-current density curves of the carbonized porous wood, the carbonized porous wood @ nickel chloride hexahydrate-thiourea/a large amount of polymers and the carbonized porous wood @ nickel chloride hexahydrate are basically rectangular, and the material has good charge-discharge cycle stability, and compared with the voltage-current density curves of the carbonized porous wood @ nickel chloride hexahydrate-thiourea/a small amount of polymers and the carbonized porous wood @ nickel chloride hexahydrate-thiourea, the voltage-current density curves have obvious redox peaks and high current density, so that nickel sulfide metal compounds in the two materials are subjected to redox reaction under the action of pulse voltage, and the energy density of the material is enhanced on the basis of carbon radicals.
As shown in fig. 7, the results of the tests on carbonized porous wood, carbonized porous wood @ nickel chloride hexahydrate-thiourea/small amount of polymer and carbonized porous wood @ nickel chloride hexahydrate-thiourea/large amount of polymer at a charge/discharge rate of 1.5A/g were measured using the charge/discharge test. The charge-discharge curve shows that the charge-discharge rates of carbonized porous wood, carbonized porous wood @ nickel chloride hexahydrate/a large amount of polymers and carbonized porous wood @ nickel chloride hexahydrate are relatively consistent, and the carbonized porous wood @ nickel chloride hexahydrate-thiourea/a small amount of polymers and carbonized porous wood @ nickel chloride hexahydrate-thiourea have longer charge-discharge time compared with the former three, which shows that nickel sulfide and carbon-based wood materials have higher energy density, and certain curve voltage drop exists in the graphs of the nickel sulfide and the carbon-based wood materials, which shows that the materials have pseudo-capacitance characteristics, which is consistent with the analysis in the graph, and metal compounds bring higher energy density for the materials.
As shown in fig. 8, the results of the tests on carbonized porous wood, carbonized porous wood @ nickel chloride hexahydrate-thiourea/a small amount of polymer and carbonized porous wood @ nickel chloride hexahydrate-thiourea/a large amount of polymer at the scanning speed of 100mv/s under the test of different potential windows indicate that the charge and discharge curves of the five-component capacitor are relatively consistent rectangles under different potential windows, which indicates that the capacitor constructed by the nickel sulfide metal compound and the carbon-based wood composite material has good cycle stability.
As shown in FIG. 9, the results of the tests on carbonized porous wood @ Nickel chloride hexahydrate-thiourea and carbonized porous wood @ Nickel chloride hexahydrate-thiourea/small amount of polymer at a charge and discharge rate of 10A/g were at 10A g-1The carbonized porous wood @ nickel chloride hexahydrate-thiourea/a small amount of polymer has higher specific capacitance, higher energy density and longer charge-discharge time. The result shows that the addition of the polymer reduces the charge-discharge expansion effect of the material, so that the material has good charge-discharge stability, and the service life of the material is prolonged.
Example 2
The invention relates to a preparation method of a 3D flowering rod-shaped nickel sulfide/wood electrode material, which comprises the following steps,
step 1, firstly, cutting wood into slices with the length of 2cm, the width of 3cm and the thickness of 3mm, weighing 0.3g of sodium chlorite and 0.5ml of glacial acetic acid, putting the weighed slices into a 100ml beaker, dissolving the weighed slices in 10ml of deionized water, and putting the prepared wood into the beaker;
obtaining delignified wood after 3 hours at the temperature of 70 ℃ and the rotating speed of 50rpm, putting the delignified wood into a refrigerator, freezing for 6 hours at the temperature of-4 ℃, and then freeze-drying for 10 hours at the temperature of-3 ℃ to obtain dried delignified wood;
step 2, preparing mixed aqueous solution with the concentration of nickel chloride hexahydrate and thiourea being 4mol/L and 3mol/L in sequence, performing ultrasonic dispersion by using a cell crushing instrument, and blowing the mixed solution of nickel chloride hexahydrate and thiourea into the treated wood by adopting a vacuum pumping and nitrogen blowing method;
putting the wood filled with the mixed aqueous solution of the nickel chloride hexahydrate and the thiourea into a refrigerator again, freezing the wood at the temperature of-4 ℃ for 6 hours, and then freezing and drying the wood at the temperature of-3 ℃ for 9 hours to obtain the dried filled wood of the nickel chloride hexahydrate and the thiourea;
step 3, putting the dried wood filled with the nickel chloride hexahydrate and the thiourea into a tube furnace, introducing air, heating to 180 ℃ at the speed of 3 ℃/min, keeping the temperature for 6 hours, introducing high-purity argon, heating to 700 ℃ at the speed of 3 ℃/min, and keeping the temperature for 2 hours again;
and (4) after the procedure is finished, opening the tube furnace when the temperature is reduced to the room temperature, and taking out the sample to obtain the 3D flowering rod-shaped nickel sulfide/wood electrode material.
Example 3
The invention relates to a preparation method of a 3D flowering rod-shaped nickel sulfide/wood electrode material, which comprises the following steps,
step 1, firstly, cutting wood into slices with the length of 4cm, the width of 1.5cm and the thickness of 4.5mm, weighing 0.5g of sodium chlorite and 12ml of glacial acetic acid, putting the weighed slices into a 100ml beaker, dissolving the weighed slices in 40ml of deionized water, and putting the prepared wood into the beaker;
obtaining delignified wood after 9 hours at 75 ℃ and the rotating speed of 300rpm, putting the delignified wood into a refrigerator, freezing for 10 hours at-3 ℃, and freeze-drying for 12 hours at-2 ℃ to obtain dried delignified wood;
step 2, preparing mixed aqueous solution with the concentration of nickel chloride hexahydrate and thiourea being 7mol/L and 5mol/L in sequence, performing ultrasonic dispersion by using a cell crushing instrument, and blowing the mixed solution of nickel chloride hexahydrate and thiourea into the treated wood by adopting a vacuum pumping and nitrogen blowing method;
putting the wood filled with the mixed aqueous solution of the nickel chloride hexahydrate and the thiourea into a refrigerator again, freezing the wood for 10 hours at the temperature of minus 3 ℃, and then freezing and drying the wood for 11 hours at the temperature of minus 2 ℃ to obtain the dried filled wood of the nickel chloride hexahydrate and the thiourea;
step 3, putting the dried wood filled with the nickel chloride hexahydrate and the thiourea into a tube furnace, introducing air, heating to 210 ℃ at the speed of 6 ℃/min, keeping the temperature for 6h, introducing high-purity argon, heating to 750 ℃ at the speed of 4 ℃/min, and keeping the temperature for 4h again;
and (4) after the procedure is finished, opening the tube furnace when the temperature is reduced to the room temperature, and taking out the sample to obtain the 3D flowering rod-shaped nickel sulfide/wood electrode material.
Example 4
The invention relates to a preparation method of a 3D flowering rod-shaped nickel sulfide/wood electrode material, which comprises the following steps,
step 1, firstly, cutting wood into slices with the length of 5cm, the width of 2cm and the thickness of 4mm, weighing 0.35g of sodium chlorite and 1ml of glacial acetic acid, putting the weighed slices into a 100ml beaker, dissolving the weighed slices in 20ml of deionized water, and putting the prepared wood into the beaker;
obtaining delignified wood after 12 hours at 85 ℃ and the rotating speed of 150rpm, putting the delignified wood into a refrigerator, freezing for 7 hours at-2 ℃, and freeze-drying for 8 hours at-4 ℃ to obtain dried delignified wood;
step 2, preparing mixed aqueous solution with the concentration of nickel chloride hexahydrate and thiourea being 6mol/L and 4mol/L in sequence, performing ultrasonic dispersion by using a cell crushing instrument, and blowing the mixed solution of nickel chloride hexahydrate and thiourea into the treated wood by adopting a vacuum pumping and nitrogen blowing method;
putting the wood filled with the mixed aqueous solution of the nickel chloride hexahydrate and the thiourea into a refrigerator again, freezing the wood at the temperature of minus 2 ℃ for 9 hours, and then freezing and drying the wood at the temperature of minus 4 ℃ for 8 hours to obtain the dried filled wood of the nickel chloride hexahydrate and the thiourea;
step 3, putting the dried wood filled with the nickel chloride hexahydrate and the thiourea into a tube furnace, introducing air, heating to 250 ℃ at the speed of 8 ℃/min, preserving heat for 6 hours, introducing high-purity argon, heating to 900 ℃ at the speed of 10 ℃/min, and preserving heat for 8 hours again;
and (4) after the procedure is finished, opening the tube furnace when the temperature is reduced to the room temperature, and taking out the sample to obtain the 3D flowering rod-shaped nickel sulfide/wood electrode material.
Example 5
The invention relates to a preparation method of a 3D flowering rod-shaped nickel sulfide/wood electrode material, which comprises the following steps,
step 1, firstly, cutting wood into slices with the length of 3cm, the width of 2.5cm and the thickness of 3.5mm, weighing 0.45g of sodium chlorite and 1.8ml of glacial acetic acid, putting the weighed slices into a 100ml beaker, dissolving the weighed slices in 50ml of deionized water, and putting the prepared wood into the beaker;
obtaining delignified wood after 10 hours at the temperature of 72 ℃ and the rotating speed of 200rpm, putting the delignified wood into a refrigerator, freezing for 8 hours at the temperature of-1 ℃, and then freeze-drying for 6 hours at the temperature of 0 ℃ to obtain dried delignified wood;
step 2, preparing mixed aqueous solution with the concentration of nickel chloride hexahydrate and thiourea being 4mol/L and 5mol/L in sequence, performing ultrasonic dispersion by using a cell crushing instrument, and blowing the mixed solution of nickel chloride hexahydrate and thiourea into the treated wood by adopting a vacuum pumping and nitrogen blowing method;
putting the wood filled with the mixed aqueous solution of the nickel chloride hexahydrate and the thiourea into a refrigerator again, freezing for 8 hours at the temperature of-1 ℃, and then freezing and drying for 6 hours at the temperature of 0 ℃ to obtain the dried filled wood of the nickel chloride hexahydrate and the thiourea;
step 3, putting the dried wood filled with the nickel chloride hexahydrate and the thiourea into a tube furnace, introducing air, heating to 360 ℃ at the speed of 9 ℃/min, keeping the temperature for 6h, introducing high-purity argon, heating to 850 ℃ at the speed of 6 ℃/min, and keeping the temperature for 10h again;
and (4) after the procedure is finished, opening the tube furnace when the temperature is reduced to the room temperature, and taking out the sample to obtain the 3D flowering rod-shaped nickel sulfide/wood electrode material.
Example 6
The invention relates to a preparation method of a 3D flowering rod-shaped nickel sulfide/wood electrode material, which comprises the following steps,
step 1, firstly, cutting wood into slices with the length of 6cm, the width of 2cm and the thickness of 5mm, weighing 0.5g of sodium chlorite and 0.8ml of glacial acetic acid, putting the weighed slices into a 100ml beaker, dissolving the weighed slices in 30ml of deionized water, and putting the prepared wood into the beaker;
obtaining delignified wood after 6 hours at the temperature of 82 ℃ and the rotating speed of 250rpm, putting the delignified wood into a refrigerator, freezing for 11 hours at the temperature of 0 ℃, and then freezing and drying for 11 hours at the temperature of-1 ℃ to obtain dried delignified wood;
step 2, preparing mixed aqueous solution with the concentration of nickel chloride hexahydrate and thiourea being 5mol/L and 6mol/L in sequence, performing ultrasonic dispersion by using a cell crushing instrument, and blowing the mixed solution of nickel chloride hexahydrate and thiourea into the treated wood by adopting a vacuum pumping and nitrogen blowing method;
putting the wood filled with the mixed aqueous solution of the nickel chloride hexahydrate and the thiourea into a refrigerator again, freezing the wood at 0 ℃ for 7 hours, and then freezing and drying the wood at-1 ℃ for 12 hours to obtain the dried filled wood of the nickel chloride hexahydrate and the thiourea;
step 3, putting the dried wood filled with the nickel chloride hexahydrate and the thiourea into a tube furnace, introducing air, heating to 300 ℃ at the speed of 10 ℃/min, keeping the temperature for 6 hours, introducing high-purity argon, heating to 800 ℃ at the speed of 8 ℃/min, and keeping the temperature for 12 hours again;
and (4) after the procedure is finished, opening the tube furnace when the temperature is reduced to the room temperature, and taking out the sample to obtain the 3D flowering rod-shaped nickel sulfide/wood electrode material.
The invention also provides a capacitor prepared by the 3D flowering rod-shaped nickel sulfide/wood electrode material, the capacitor is assembled simply, a diaphragm is arranged between the electrode materials of the same material or different component materials, the two electrode materials which are both 3D flowering rod-shaped nickel sulfide/wood are adopted for assembly, and the 3D flowering rod-shaped nickel sulfide/wood and a metal electrode or a conductive polymer electrode can be assembled.
The invention also provides electronic equipment with the energy battery, after the capacitor is assembled, the anode and the cathode of the capacitor are connected with the electronic equipment capable of being connected, and the electronic equipment can be driven to normally work under the condition of meeting the requirements of the voltage and the current of the equipment and has the same function as the battery.
The wood without the lignin has a large specific surface area, is a 3D material containing a large number of pore channel structures, and a large number of generated space structures provide more effective pore channel microstructures for the material, so that nickel sulfide directly grows on the wood without the lignin, the wood after high-temperature treatment is loose and porous, ordered pore channels are formed in the wood, metal can grow, the surface of the wood can also grow in the growth process, and the whole material is soaked in a metal solution and then taken out for treatment; the electrode material is used after being assembled into a capacitor, the wooden pore channel is loose, porous and fragile after high-temperature reduction, the capacitor needs to be recycled for many times, external forces such as compression and bending in the using process can damage the material, the pore channel filled metal plays a certain supporting role, structural collapse caused in the circulating process is avoided, the electrochemical stability of the material is improved, the transmission capacity and the storage capacity of electric charge are improved to a certain extent, and the electric conductivity and the electrochemical performance of the material are greatly improved.
The invention adopts CVD method to prepare nickel sulfide/wood composite material, selects thiourea as sulfur source, nickel chloride hexahydrate as nickel source, processes wood, uses vacuum pumping and air blowing method to blow nickel chloride hexahydrate and thiourea aqueous solution into pore channel of wood, dries them, and then insulates oxygen at high temperature, makes blossoming rod-shaped nickel sulfide grow uniformly on pore channel and surface of wood, improves transmission quantity of electron, improves conductivity and structural stability of material, reduces internal resistance of material, improves conductivity of material, improves energy storage property of material, and improves structural stability and energy storage property of nickel sulfide material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the embodiments of the present invention.
Claims (10)
1. A preparation method of a 3D flowering rod-shaped nickel sulfide/wood electrode material is characterized by comprising the following steps,
step 1, mixing the following components in a molar concentration ratio of (4-7): (3-6) filling the mixed solution of nickel chloride and thiourea in delignified wood to obtain delignified wood containing the mixed solution;
step 2, removing water in the delignified wood containing the mixed solution to obtain dry filled wood;
and 3, firstly, preserving heat of the dried filling wood at 180-360 ℃ for 3-6 h in an oxygen environment, and then preserving heat at 700-900 ℃ for 2-5 h in an oxygen-free environment to obtain the 3D flowering rod-shaped nickel sulfide/wood electrode material.
2. The method for preparing the 3D flowering rod-shaped nickel sulfide/wood electrode material according to claim 1, wherein in the step 1, the delignified wood is obtained by the following steps,
step 1a, soaking wood in a mixed aqueous solution of sodium chlorite and glacial acetic acid, and taking out the wood after the wood is kept for 3-12 hours at the temperature of 70-85 ℃;
and step 1b, freezing the wood obtained in the step 1a at the temperature of below-5 ℃ for 6-12 h, and then carrying out freeze drying at the temperature of below-5 ℃ for 5-12 h to obtain delignified wood.
3. The preparation method of the 3D flowering rod-shaped nickel sulfide/wood electrode material as claimed in claim 2, wherein in the step 1a, the wood is cuboid, 2-6 cm long, 1-3 cm wide and 2-5 mm thick;
in the mixed solution of sodium chlorite and glacial acetic acid, the ratio of the sodium chlorite to the glacial acetic acid to the deionized water is (0.3-0.5) g: (0.5-2) ml: (10-50) ml.
4. The method for preparing the 3D flowering rod-shaped nickel sulfide/wood electrode material according to claim 2, wherein in the step 1a, the wood is soaked in a mixed solution of sodium chlorite and glacial acetic acid at a rotating speed of 50-300 rpm.
5. The method for preparing the 3D flowering rod-shaped nickel sulfide/wood electrode material as claimed in claim 1, wherein in the step 1, a mixed solution of nickel chloride and thiourea is blown into delignified wood by a vacuum-pumping nitrogen blowing method, so as to obtain the delignified wood containing the mixed solution.
6. The method for preparing the 3D flowering rod-shaped nickel sulfide/wood electrode material as claimed in claim 1, wherein in the step 2, dried filling wood is obtained by the following process,
and (3) freezing the delignified wood containing the mixed solution at the temperature of below-5 ℃ for 6-12 h, and then freezing and drying the delignified wood at the temperature of below-5 ℃ for 5-12 h to obtain the dried filled wood.
7. The method for preparing a 3D flowering rod-shaped nickel sulfide/wood electrode material as claimed in claim 1, wherein in the step 3, the temperature of the dried filled wood is raised to 180-360 ℃ at a rate of 3-10 ℃/min, and then raised to 700-900 ℃ at a rate of 3-10 ℃/min.
8. A3D flowering rod-shaped nickel sulfide/wood electrode material obtained by the preparation method of the 3D flowering rod-shaped nickel sulfide/wood electrode material as claimed in any one of claims 1 to 7.
9. A capacitor comprising the 3D flowering rod of nickel sulfide/wood electrode material of claim 8.
10. An electronic device driven by the capacitor of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911102278.9A CN110931266B (en) | 2019-11-12 | 2019-11-12 | 3D flowering rod-shaped nickel sulfide/wood electrode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911102278.9A CN110931266B (en) | 2019-11-12 | 2019-11-12 | 3D flowering rod-shaped nickel sulfide/wood electrode material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110931266A true CN110931266A (en) | 2020-03-27 |
| CN110931266B CN110931266B (en) | 2021-04-20 |
Family
ID=69852709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911102278.9A Active CN110931266B (en) | 2019-11-12 | 2019-11-12 | 3D flowering rod-shaped nickel sulfide/wood electrode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110931266B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111463028A (en) * | 2020-04-09 | 2020-07-28 | 陕西科技大学 | rGO-L iOH micro-spring/wood composite electrode material, and preparation method and application thereof |
| CN113314349A (en) * | 2021-06-24 | 2021-08-27 | 北华大学 | Polyacrylonitrile/wood-based derived carbon porous material and preparation and application thereof |
| CN114597079A (en) * | 2022-01-30 | 2022-06-07 | 浙江工业大学 | Carbon-based transition metal oxide electrode material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109225343A (en) * | 2018-10-17 | 2019-01-18 | 华南理工大学 | A kind of delignification wood chip/Fe3O4Composite material and preparation method and application |
| CN110060873A (en) * | 2019-04-17 | 2019-07-26 | 齐鲁工业大学 | The hollow biological carbon ball base nanometer nickel sulfide rod supercapacitor of one kind and preparation method |
| CN110379646A (en) * | 2019-07-25 | 2019-10-25 | 中南林业科技大学 | A kind of preparation method based on two selenizing molybdenums/charcoal Asymmetric Supercapacitor |
| CN110405883A (en) * | 2019-07-24 | 2019-11-05 | 北京林业大学 | It is a kind of to be alkylated energy storage timber of the boron nitride as filler |
| CN110587752A (en) * | 2019-09-17 | 2019-12-20 | 北京林业大学 | Energy storage wood construction method taking alkylated carbon black as filler |
-
2019
- 2019-11-12 CN CN201911102278.9A patent/CN110931266B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109225343A (en) * | 2018-10-17 | 2019-01-18 | 华南理工大学 | A kind of delignification wood chip/Fe3O4Composite material and preparation method and application |
| CN110060873A (en) * | 2019-04-17 | 2019-07-26 | 齐鲁工业大学 | The hollow biological carbon ball base nanometer nickel sulfide rod supercapacitor of one kind and preparation method |
| CN110405883A (en) * | 2019-07-24 | 2019-11-05 | 北京林业大学 | It is a kind of to be alkylated energy storage timber of the boron nitride as filler |
| CN110379646A (en) * | 2019-07-25 | 2019-10-25 | 中南林业科技大学 | A kind of preparation method based on two selenizing molybdenums/charcoal Asymmetric Supercapacitor |
| CN110587752A (en) * | 2019-09-17 | 2019-12-20 | 北京林业大学 | Energy storage wood construction method taking alkylated carbon black as filler |
Non-Patent Citations (2)
| Title |
|---|
| PENG-FEI YIN ET AL.: "Large-scale synthesis of nickel sulfide micro/nanorods via a hydrothermal process", 《INTERNATIONAL JOURNAL OF MINERALS, METALLURGY AND MATERIALS》 * |
| 吴俊凯 等: "N13 S4花状分等级微/纳米结构及其在高性能超级电容器中的应用", 《安徽工程大学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111463028A (en) * | 2020-04-09 | 2020-07-28 | 陕西科技大学 | rGO-L iOH micro-spring/wood composite electrode material, and preparation method and application thereof |
| CN111463028B (en) * | 2020-04-09 | 2021-06-29 | 陕西科技大学 | rGO-LiOH micro-spring/wood composite electrode material and preparation method and application thereof |
| CN113314349A (en) * | 2021-06-24 | 2021-08-27 | 北华大学 | Polyacrylonitrile/wood-based derived carbon porous material and preparation and application thereof |
| CN114597079A (en) * | 2022-01-30 | 2022-06-07 | 浙江工业大学 | Carbon-based transition metal oxide electrode material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110931266B (en) | 2021-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110931266B (en) | 3D flowering rod-shaped nickel sulfide/wood electrode material and preparation method and application thereof | |
| CN104733700B (en) | Preparation method of flexible anode of lithium-selenium battery | |
| CN109081340B (en) | Pine-based biomass activated carbon, preparation method thereof and application thereof in electrochemical energy storage | |
| CN111293301B (en) | Soft and hard carbon composite porous negative electrode material for sodium ion battery and preparation method thereof | |
| CN103569997A (en) | Preparation method for flexible graphene-modified knittable carbon nanofiber | |
| CN108862235A (en) | A kind of hollow hard carbon material of threadiness and preparation method thereof can be used for sodium-ion battery cathode | |
| CN111725489B (en) | Element-doped conductive composite carbonized material and preparation method and application thereof | |
| CN110364366A (en) | A kind of high-performance electric chemistry capacitor anode material molybdenum dioxide and nitrogen-doped carbon composite material and preparation method and application | |
| CN112897499A (en) | Method for preparing double-heterogeneous-element-doped porous carbon material by salt template method | |
| CN107887174A (en) | The method that porous carbon electrode material is prepared using root system of plant | |
| CN111137890A (en) | Preparation method of biomass hierarchical pore nano-ring microstructure carbon-based supercapacitor electrode material | |
| CN110212180A (en) | A kind of preparation method and lithium-sulfur cell of lithium sulfide self-supporting carbon ball/carbon nano-fiber composite material | |
| CN111370702A (en) | Application of self-supporting porous hollow carbon fiber membrane | |
| CN112299388A (en) | Ordered microporous carbon, preparation method thereof and application thereof in sodium ion capacitor | |
| CN109637843A (en) | A method of supercapacitor is prepared by electrode material of celery | |
| CN114204218A (en) | Loaded hollow Co3O4Preparation method of positive electrode side interlayer for cubic lithium-sulfur battery | |
| CN112239201A (en) | Method for preparing nitrogen-sulfur double-doped porous carbon through one-step carbonization | |
| CN107881600B (en) | Preparation method and application of nano carbon fiber for lithium ion battery cathode | |
| CN111599601B (en) | Lithium-sodium ion composite porous carbon-based material and preparation method and application thereof | |
| CN109650373B (en) | Copper-loaded sodium alginate carbon aerogel and preparation method and application thereof | |
| CN111785531A (en) | Preparation method of carbon nanotube/bacterial cellulose aerogel material and super capacitor | |
| CN106058254A (en) | Method for preparing biochar/carbon nano-tubes for cathode materials for sodium ion batteries | |
| CN113200544B (en) | Preparation method of biomass charcoal-based supercapacitor electrode material | |
| CN112290025B (en) | Preparation method of electrode material based on carbonized kelp and lithium-sulfur battery | |
| CN113675003B (en) | Preparation and application of kelp-derived porous carbon loaded cobalt phosphide and cobalt phosphate electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220822 Address after: Room 11008, Unit 1, Building 12, Tai'ao Plaza, No. 275, Fenghe Road, Lianhu District, Xi'an City, Shaanxi Province 710077 Patentee after: Xi'an Huabo Electronic Technology Co.,Ltd. Address before: 710021 Shaanxi province Xi'an Weiyang University Park Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY |