CN108630918A - A kind of highdensity metal oxide of self-supporting/nitrogen-doped graphene combination electrode and its preparation method and application - Google Patents
A kind of highdensity metal oxide of self-supporting/nitrogen-doped graphene combination electrode and its preparation method and application Download PDFInfo
- Publication number
- CN108630918A CN108630918A CN201810301529.5A CN201810301529A CN108630918A CN 108630918 A CN108630918 A CN 108630918A CN 201810301529 A CN201810301529 A CN 201810301529A CN 108630918 A CN108630918 A CN 108630918A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- doped graphene
- metal oxide
- graphene
- self
- 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
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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses a kind of highdensity metal oxide of self-supporting/nitrogen-doped graphene combination electrode and its preparation method and application.The combination electrode obtains nitrogen-doped graphene by water-bath first, again in organic solvent by nitrogen-doped graphene dispersion, the organic solvent dissolved with metal salt is added dropwise, hydro-thermal reaction is carried out after being uniformly dispersed, powdery metal oxide/nitrogen-doped graphene composite material is made；Small amounts graphene is added, metal oxide/nitrogen-doped graphene composite material is made to be uniformly dispersed in graphene oxide, metal oxide/nitrogen-doped graphene hydrogel is made by secondary hydro-thermal reaction, is finally made by slice, natural shrinkage drying.There is the composite material of the present invention self supporting structure, density to be more than 1.0g/cm3, the electrode slice that is obtained by two one-step hydrothermals can directly as lithium ion battery or the electrode of sodium-ion battery, realize its high volume capacity, high invertibity and high rate capability chemical property.
Description
Technical field
It is highdensity more particularly, to a kind of self-supporting the invention belongs to nano material self-supporting device arts
Metal oxide/nitrogen-doped graphene combination electrode and its preparation method and application.
Background technology
It is solved currently, new energy field is faced with many problems demands, wherein the energy density high power of lithium ion battery
Density is low, and ultracapacitor power density high-energy density is low, how by lithium ion battery with ultracapacitor the advantages of it is comprehensive
Altogether, become the hot spot that researchers study.Many carbon nano-electrode material porositys are high, but density is very low, causes
Material internal has a large amount of space to be filled by electrolyte, increases only the weight of device and does not contribute capacity, to drag down
The performance of entire device, meanwhile, lower density means that active material quality is smaller in the space of restriction, leads to electrode
The volume energy density of material and entire energy storage system is very limited.Therefore, high-density electrode material is developed, electrode space is improved
Utilization rate is to realize that the important channel of fine and close energy storage, high-density electrode material can have high-energy in small size material, can expire
The higher and higher energy storage requirement of sufficient people, promotes the hair in the fields such as mobile electronic device, electric vehicle, large scale electric network design
Exhibition pushes the practicalization of next-generation energy storage device.
Invention content
In order to solve above-mentioned the deficiencies in the prior art and disadvantage, a kind of highdensity metal oxidation of self-supporting is provided
Object/nitrogen-doped graphene combination electrode.The combination electrode has self supporting structure, and wherein graphene oxide is as binder, gold
Belong to oxide/nitrogen-doped graphene dusty material as active material, takes full advantage of the advantage of material..
It is a further object of the present invention to provide the highdensity metal oxide of above-mentioned self-supporting/nitrogen-doped graphene compound electrics
The preparation method of pole, this method make metal oxide growth in situ uniform load in nitrogen-doped graphene by hydrothermal reaction at low temperature
On, and average-size is 2-6nm, then dry united method by secondary hydro-thermal, slice, natural shrinkage and prepare dusty material
Lithium battery or sode cell electrode plates are directly used as, dusty material is solved and is used as pole piece without adding binder at hydrogel
The problems such as easy to fall off, easy crushing, resistance is big in charge and discharge process, poor circulation.
Another object of the present invention is to provide the highdensity metal oxide of above-mentioned self-supporting/nitrogen-doped graphene compound electric
The application of pole.
The purpose of the present invention is realized by following technical proposals：
A kind of highdensity metal oxide of self-supporting/nitrogen-doped graphene combination electrode, the combination electrode is first
Nitrogen-doped graphene is obtained by water-bath, then in organic solvent by nitrogen-doped graphene dispersion, is added dropwise dissolved with metal salt
Organic solvent, after being uniformly dispersed carry out hydro-thermal reaction I, be made powdery metal oxide/nitrogen-doped graphene composite material；
Small amounts graphene solution is added, metal oxide/nitrogen-doped graphene composite material is made to disperse in graphene oxide
Uniformly, metal oxide/nitrogen-doped graphene hydrogel is made by secondary hydro-thermal reaction II, finally wrinkled by slice, naturally
Contracting is dry to be made.
Preferably, the solution concentration of the metal salt is 0.01~0.8mol/L；The mole and oxygen of the metal salt
The mass ratio of graphite alkene is (0.01~0.1) mol：1g, a concentration of 1.5~3mg/ml of the graphene oxide solution.
Preferably, the organic solvent is absolute ethyl alcohol, acetone, ether or isopropanol.
Preferably, the metal salt is titanium salt, pink salt, antimonic salt or molysite.
It is further preferable that the titanium salt is one or more of titanium tetrachloride, phthalic acid or Titanium Nitrate；The pink salt
For one or more of stannic chloride, stannous chloride, nitric acid tin, STANNOUS SULPHATE CRYSTALLINE or nitric acid stannous；The antimonic salt is antimony chloride, sulfuric acid
One or more of antimony or sour antimony；The molysite be in iron chloride, ferric nitrate, ferrous sulfate or ferrous nitrate it is a kind of with
On.
Preferably, the temperature of the water-bath is 90~120 DEG C；The temperature of the hydro-thermal reaction I is 100~130 DEG C,
The time of the hydro-thermal reaction I is 0.5~8h；The temperature of the hydro-thermal reaction II is 160~220 DEG C, the hydro-thermal reaction II
Time be 6~for 24 hours.
The preparation method of the highdensity metal oxide of the self-supporting/nitrogen-doped graphene combination electrode, including such as
Lower specific steps：
S1. under the conditions of magnetic agitation, rich nitrogen reagent aqueous solution is added dropwise into graphene oxide water solution, waits being uniformly dispersed
Afterwards, water-bath is carried out, and continues to stir, then by filtering, drying, obtains nitrogen-doped graphene
S2. nitrogen-doped graphene is evenly dispersed in organic solvent, then successively it is added dropwise dissolved with the organic molten of metal salt
Agent and deionized water carry out hydro-thermal reaction I after stirring a period of time in water heating kettle, then through suction filtration, drying, washing, obtain gold
Belong to oxide/nitrogen-doped graphene powder；
S3. graphene oxide dispersion is formed into dispersion liquid A, step S2 gained metal oxide/N dopings in aqueous solution
Graphene powder is dispersed in formation dispersion liquid B in ethanol solution, then dispersion liquid B is added dropwise in dispersion liquid A, is uniformly dispersed
Afterwards, secondary hydro-thermal reaction II is carried out in water heating kettle, obtains metal oxide/nitrogen-doped graphene hydrogel；
S4. hydrogel obtained by step S3 is cut into electrode slice, natural shrinkage drying obtains the highdensity gold oxidation of self-supporting
Object/nitrogen-doped graphene combination electrode.
Preferably, the rich nitrogen reagent in step S1 is in cyanamide, triethylamine, urea, azodiisobutyronitrile or aniline
A kind of or two kinds arbitrary, the time of the water-bath is 6~36h；Metal oxide/nitrogen-doped graphene described in step S2
The average grain diameter of metal oxide is 2~6nm in powder.
Preferably, graphene oxide described in step S3 is 15~20wt% of hydrogel gross mass, graphene oxide
A concentration of 1.5~3mg/ml；Dry temperature described in step S4 is 20~40 DEG C, and the time of the drying is 12~60h.
The highdensity metal oxide of the self-supporting/nitrogen-doped graphene combination electrode lithium ion battery or sodium from
Application in sub- field of batteries.
In general, high-energy density and high power density often require that material can store a large amount of charges and one can be with
The electrode structure of fast charging and discharging, graphene hydrogel is very loose, has porous structure and good electric conductivity, is conducive to lithium
The free diffusing of ion and charge in charge and discharge process, and there is high-specific surface area, it is ensured that leaching of the electrolyte to electrode
Profit degree, abundant pore structure provide express passway for the transmission of lithium ion, shorten ion transmission distance discrete time, while water-setting
It is tridimensional network inside glue, the cushion space of bigger can be provided for the volume expansion of metal oxide particle, maintains electrode
The stability of structure is a kind of lithium ion battery negative material being very suitable for high current charge-discharge.On the other hand, conventional powder
Material need to add binder, can just obtain electrode plates by preparing slurry and coating, resistance is big in charge and discharge process, and energy is close
It spends low, and phenomena such as easily fall off, crush, causes capacity attenuation serious, high rate performance is low；And hydrogel is bonded without adding
Agent, can be directly used as electrode plates, method simply can scale, resistance is small in charge and discharge process, and energy density is high, it can be achieved that high
Cycle performance, high rate capability and high coulombic efficiency.
The present invention is by hydrothermal reaction at low temperature, using nitrogen-doped graphene as carbon material carrier, on nitrogen-doped graphene surface
Fixed nano metal nano particle, nitrogen-doped graphene provide abundant active site, make metal oxide in its surface in situ
Homoepitaxial, not only can avoid the reunion of graphene, but also can control the particle size of metal oxide and reach nanoscale, to inhibit
The volume expansion of metal oxide, avoids active material from falling off in charge and discharge process, reduces capacity attenuation, in addition N doping graphite
Alkene can provide abundant pore structure, effectively reduce the electron transmission resistance of metal oxide nanoparticles, enhance lithium battery and surpass
The high rate performance and cycle performance of grade capacitor.Again by secondary hydro-thermal, metal oxide/nitrogen-doped graphene dusty material is equal
It is even to be supported on the three-dimensional network carbon material of graphene oxide formation, the highdensity hydrogel combination electrode of self-supporting is formed,
Middle graphene oxide tridimensional network provides express passway for the transmission of lithium ion, shortens diffusion length and time, rich
Rich pore structure promotes the infiltration of electrolyte, increases lithium ion and charge and metal oxide/nitrogen-doped graphene powder
The contact area of material activity substance, on the other hand, hydrogel pole piece can be directly used as electrode without adding binder, maintain
The stability of electrode solves the problems, such as dusty material easy to fall off, easy crushing as pole piece, is shown in charge and discharge process excellent
Different chemical property.
Compared with prior art, the invention has the advantages that：
1. metal oxide prepared by the present invention/nitrogen-doped graphene combination electrode has the characteristics that self-supporting is highdensity,
Compared with dusty material, hydrogel combination electrode is high-density electrode, can effectively improve electrode space utilization rate, small as possible
Capacity high as possible is stored under volume, improves the energy density of electrode, meets the energy storage demand of people.
2. the present invention is using the abundant oxygen-containing functional group of surface of graphene oxide, using the method for N doping to graphite oxide
Modification is fixed in alkene surface, and compared with non-nitrogen-doped graphene, nitrogen-doped graphene not only maintains graphene high-specific surface area
The characteristics of, also there are more active sites, can effectively inhibit the volume expansion of metal oxide, uniformly fix extra small metal oxygen
Compound effectively solves the problems, such as that metal oxide is easily reunited.It is easily taken off as pole piece in addition, combination electrode can also solve dusty material
The problem of falling, easily crushing, this preparation method is simple, can be mass-produced, and has very important practical application meaning.
3. the present invention is reacted by low-temperature hydrothermal, using the active site that nitrogen-doped graphene surface is abundant, fixed metal
The growth in situ of oxide makes the control of its average grain diameter in 2~6nm；15~20% graphene oxides are re-introduced into as binder,
By secondary hydro-thermal reaction, the highdensity hydrogel combination electrode of self-supporting is formed.It is applied with conventional powder material addition binder
Pole piece made from cloth is compared, and the hydrogel pole piece obtained after sliced and natural shrinkage had both maintained metal oxide/N doping
Material character of the Graphene powder powder material as active material, and it can be directly used as electrode without adding binder, it reduces and fills
Discharge resistance shows the superior electrifications such as macroion electrons spread rate, high invertibity, high circulation in electro-chemical test
Learn performance.
Description of the drawings
Fig. 1 is the TiO of 1 gained of embodiment2Self supporting structure light before and after the combination electrode nature shrinkage of/nitrogen-doped graphene
Learn photo.
Fig. 2 is 1 gained TiO of embodiment2/ nitrogen-doped graphene combination electrode, TiO2The X of/nitrogen-doped graphene dusty material
X ray diffration pattern x.
Fig. 3 is 1 gained TiO of embodiment2The low resolved transmittance electromicroscopic photograph of/nitrogen-doped graphene combination electrode.
Fig. 4 is 1 gained TiO of embodiment2The high-resolution-ration transmission electric-lens photo of/nitrogen-doped graphene combination electrode.
Fig. 5 is 1 gained TiO of embodiment2/ nitrogen-doped graphene combination electrode is negative electrode of lithium ion battery, in 0.6C charge and discharges
Cyclical stability under electric multiplying power.
Specific implementation mode
The content further illustrated the present invention with reference to specific embodiment, but should not be construed as limiting the invention.
Embodiment 1
1. preparing
S1. under the conditions of magnetic agitation, to 200ml 0.5mg ml-18ml cyanamide water is added dropwise in graphene oxide water solution
Solution is transferred to after being uniformly dispersed in 250ml three-necked flasks, and for 24 hours, and continued mechanical stirs 90 DEG C of water-baths, then passes through
Vacuum filtration, drying, obtain nitrogen-doped graphene；
S2. it weighs the stirring of 30mg nitrogen-doped graphenes or ultrasound is dispersed in 185ml absolute ethyl alcohols, be then added dropwise
3.3ml 0.55mol l-1Dissolved with TiCl4Ethanol solution, then 4ml deionized waters are added dropwise, stir after a period of time
120 DEG C of hydro-thermal reaction 2h in 200ml water heating kettles, then through suction filtration, drying, washing, obtain TiO2/ nitrogen-doped graphene powder material
Material；
S3. by 28ml 4.5mg ml-1Graphene oxide be dispersed in 25ml aqueous solutions, weigh the production in 714mg S2
Object disperses in 20ml ethanol solutions, then the latter's dispersant liquid drop is added in the former dispersion liquid, after being uniformly dispersed, in 50ml water
180 DEG C of secondary hydro-thermal reaction 12h, obtain TiO in hot kettle2/ nitrogen-doped graphene hydrogel；
S4. the hydrogel in step S3 is cut into pole piece size, 25 DEG C of natural shrinkages are dried 36h, obtained viscous without addition
Tie the high density TiO of agent2/ nitrogen-doped graphene composite electrode pole piece.
2. performance evaluation
After tested, Fig. 1 is above-mentioned prepared TiO2The optics of/nitrogen-doped graphene combination electrode self supporting structure shines
Piece.From fig. 1, it can be seen that the combination electrode has self supporting structure, can natural shrinkage form pole piece, pass through the volume after measuring shrinkage
And quality, it is 1.8mg/cm that its density, which is calculated,3.Fig. 2 is above-mentioned prepared TiO2/ nitrogen-doped graphene hydrogel,
TiO2The X-ray diffractogram of/nitrogen-doped graphene dusty material；As can be seen from Figure 2, the XRD of titanium dioxide is included in the hydrogel
Peak and graphitic carbon peak, it was demonstrated that the hydrogel includes titanium dioxide and graphene.Fig. 3 and Fig. 4 is above-mentioned prepared TiO2/ nitrogen is mixed
The low resolution (× 30k times) of miscellaneous graphene hydrogel and high-resolution (× 200k times) transmission electron microscope photo.It is found that it should from Fig. 3 and 4
Nano particle in hydrogel is presented high density and is evenly distributed in nitrogen-doped graphene surface, as can be seen from Figure 4, in the hydrogel
Nano particle show TiO2(101) lattice fringe of crystal face, interplanar distance 0.35nm, and grain size are 5nm or so, card
The nano particle of actual loading is TiO2Extra granular.Fig. 5 is above-mentioned prepared TiO2/ nitrogen-doped graphene hydrogel is as lithium
Ion battery cathode, the cyclical stability under 0.6C charge-discharge magnifications；As can be seen from Figure 5, after 100 circle of cycle, above-mentioned water-setting
Gel electrode still keeps the specific capacity of 185mAh/g, illustrates that the water-setting gel electrode shows good cyclical stability.
Embodiment 2
1. preparing
S1. under the conditions of magnetic agitation, 8ml triethylamine aqueous solutions is added dropwise into 100mg graphene oxide water solutions, wait disperseing
It after uniformly, is transferred in 250ml three-necked flasks, 110 DEG C of water-bath 6h, and continued mechanical stirs, then by being filtered by vacuum, doing
It is dry, obtain nitrogen-doped graphene；
S2. it weighs the stirring of 30mg nitrogen-doped graphenes or ultrasound is dispersed in 185ml acetone, 4ml is then added dropwise
0.6mol l-1Dissolved with Fe (NO3)3Acetone soln, then 4ml deionized waters are added dropwise, stir after a period of time in 200ml water heating kettles
In 130 DEG C of hydro-thermal reaction 4h, then through suction filtration, drying, washing, obtain Fe2O3/ nitrogen-doped graphene dusty material；
S3. by 30ml 4.2mg ml-1Graphene oxide be dispersed in 25ml aqueous solutions, weigh the production in 504mg S2
Object disperses in 20ml ethanol solutions, then the latter's dispersant liquid drop is added in the former dispersion liquid, after being uniformly dispersed, in 50ml water
190 DEG C of secondary hydro-thermal reaction 6h, obtain Fe in hot kettle2O3/ nitrogen-doped graphene hydrogel；
S4. the hydrogel in step S3 is cut into pole piece size, 30 DEG C of natural shrinkages are dried 48h, obtained viscous without addition
Tie the high density Fe of agent2O3/ nitrogen-doped graphene composite electrode pole piece.
2. performance evaluation
After tested, the density of above-mentioned combination electrode is 1.3g/cm3, Fe in above-mentioned hydrogel2O3Nano particle uniform load
On nitrogen-doped graphene, average grain diameter is about 5.6nm, at discharge current density 0.1A/g, the reversible ratio after recycling 100 times
Capacity is about 885mAh/g, and capacity retention ratio is up to 97.9%.
Embodiment 3
1. preparing
S1. under the conditions of magnetic agitation, 4g aqueous solution of urea is added dropwise into 100mg graphene oxide water solutions, waits for that dispersion is equal
It after even, is transferred in 250ml three-necked flasks, 95 DEG C of water-bath 28h, and continued mechanical stirs, then by being filtered by vacuum, doing
It is dry, obtain nitrogen-doped graphene；
S2. it weighs the stirring of 30mg nitrogen-doped graphenes or ultrasound is dispersed in 185ml isopropanols, be then added dropwise
2.6ml 0.75mol l-1Dissolved with Sn (SO4)2Aqueous isopropanol, then 4ml deionized waters are added dropwise, stir after a period of time
110 DEG C of hydro-thermal reaction 5h in 200ml water heating kettles, then through suction filtration, drying, washing, obtain SnO2/ nitrogen-doped graphene powder material
Material；
S3. by 20ml 4.5mg ml-1Graphene oxide be dispersed in 25ml aqueous solutions, weigh the production in 390mg S2
Object disperses in 20ml ethanol solutions, then the latter's dispersant liquid drop is added in the former dispersion liquid, after being uniformly dispersed, in 50ml water
180 DEG C of secondary hydro-thermal reactions for 24 hours, obtain SnO in hot kettle2/ nitrogen-doped graphene hydrogel；
S4. the hydrogel in step S3 is cut into pole piece size, 40 DEG C of natural shrinkages are dried 18h, obtained viscous without addition
Tie the high density SnO of agent2/ nitrogen-doped graphene composite electrode pole piece.
2. performance evaluation
After tested, the density of above-mentioned combination electrode is 1.0g/cm3, SnO in above-mentioned hydrogel2Nano particle uniform load exists
On nitrogen-doped graphene, average grain diameter is about 5nm, at discharge current density 0.1A/g, the reversible specific capacity after recycling 100 times
About 842mAh/g, capacity retention ratio are up to 97.5%.
Embodiment 4
1. preparing
S1. under the conditions of magnetic agitation, 8ml aniline-water solutions are added dropwise into 100mg graphene oxide water solutions, wait for that dispersion is equal
It after even, is transferred in 250ml three-necked flasks, 120 DEG C of water-bath 8h, and continued mechanical stirs, then by being filtered by vacuum, doing
It is dry, obtain nitrogen-doped graphene；
S2. it weighs the stirring of 30mg nitrogen-doped graphenes or ultrasound is dispersed in 185ml ether, 3.3ml is then added dropwise
0.55mol l-1Dissolved with Ti (NO3)4Diethyl ether solution, then 4ml deionized waters are added dropwise, stir after a period of time in 200ml hydro-thermals
125 DEG C of hydro-thermal reaction 0.5h in kettle, then through suction filtration, drying, washing, obtain TiO2/ nitrogen-doped graphene dusty material；
S3. by 16ml 4.8mg ml-1Graphene oxide be dispersed in 25ml aqueous solutions, weigh in 358.4mg S2
Product disperses in 20ml ethanol solutions, then the latter's dispersant liquid drop is added in the former dispersion liquid, after being uniformly dispersed, in 50ml
200 DEG C of secondary hydro-thermal reaction 12h, obtain TiO in water heating kettle2/ nitrogen-doped graphene hydrogel；
S4. the hydrogel in step S3 is cut into electrode slice, 25 DEG C of natural shrinkages dry 60h, obtain bonding without adding
The high density TiO of agent2/ nitrogen-doped graphene composite electrode pole piece.
2. performance evaluation
After tested, the density of above-mentioned combination electrode is 1.2mg/cm3, TiO in above-mentioned hydrogel2Nano particle uniform load
On nitrogen-doped graphene, average grain diameter is about 3.8nm, at discharge current density 0.1A/g, the reversible ratio after recycling 100 times
Capacity is about 205mAh/g, and capacity retention ratio is up to 94.7%.
Embodiment 5
1. preparing
S1. under the conditions of magnetic agitation, 8ml aniline-water solutions are added dropwise into 100mg graphene oxide water solutions, wait for that dispersion is equal
It after even, is transferred in 250ml three-necked flasks, 120 DEG C of water-bath 12h, and continued mechanical stirs, then by being filtered by vacuum, doing
It is dry, obtain nitrogen-doped graphene；
S2. it weighs the stirring of 30mg nitrogen-doped graphenes or ultrasound is dispersed in 185ml ether, 4.6ml is then added dropwise
0.35mol l-1Dissolved with SnCl2Diethyl ether solution, then 4ml deionized waters are added dropwise, stir after a period of time in 200ml water heating kettles
120 DEG C of hydro-thermal reaction 6h, then through suction filtration, drying, washing, obtain SnO/ nitrogen-doped graphene dusty materials；
S3. by 12ml 6.5mg ml-1Graphene oxide be dispersed in 25ml aqueous solutions, weigh in 426.5mg S2
Product disperses in 20ml ethanol solutions, then the latter's dispersant liquid drop is added in the former dispersion liquid, after being uniformly dispersed, in 50ml
220 DEG C of secondary hydro-thermal reaction 18h in water heating kettle, obtain SnO/ nitrogen-doped graphene hydrogels；
S4. the hydrogel in step S3 is cut into electrode slice, 20 DEG C of natural shrinkages dry 60h, obtain bonding without adding
The high density SnO/ nitrogen-doped graphene composite electrode pole pieces of agent.
2. performance evaluation
After tested, the density of above-mentioned combination electrode is 1.5mg/cm3, SnO nano particle uniform loads in above-mentioned hydrogel
On nitrogen-doped graphene, average grain diameter is about 5.9nm, under discharge current density 0.1A/g, the reversible specific volume after cycle 100 times
Amount is about 1226mAh/g, and capacity retention ratio is up to 94.8%.
Embodiment 6
1. preparing
S1. under the conditions of magnetic agitation, to 200ml 0.5mg ml-1It is different that 8ml azos two are added dropwise in graphene oxide water solution
Butyronitrile aqueous solution is transferred to after being uniformly dispersed in 250ml three-necked flasks, 90 DEG C of water-bath 36h, and continued mechanical stirs,
Again by being filtered by vacuum, drying, nitrogen-doped graphene is obtained；
S2. it weighs the stirring of 30mg nitrogen-doped graphenes or ultrasound is dispersed in 185ml isopropanols, be then added dropwise
2.6ml 0.55mol l-1Dissolved with SbCl4Aqueous isopropanol, then 4ml deionized waters are added dropwise, stir after a period of time in 200ml
115 DEG C of hydro-thermal reaction 8h in water heating kettle, then through suction filtration, drying, washing, obtain Sb2O3/ nitrogen-doped graphene dusty material；
S3. by 23ml 6.3mg ml-1Graphene oxide be dispersed in 25ml aqueous solutions, weigh in 569.1mg S2
Product disperses in 20ml ethanol solutions, then the latter's dispersant liquid drop is added in the former dispersion liquid, after being uniformly dispersed, in 50ml
190 DEG C of secondary hydro-thermal reaction 8h, obtain Sb in water heating kettle2O3/ nitrogen-doped graphene hydrogel；
S4. the hydrogel in step S3 is cut into pole piece size, 35 DEG C of natural shrinkages are dried 12h, obtained viscous without addition
Tie the high density Sb of agent2O3/ nitrogen-doped graphene composite electrode pole piece.
2. performance evaluation
After tested, the density of above-mentioned combination electrode is 1.6mg/cm3, Sb in above-mentioned hydrogel2O3Nano particle uniform load
On nitrogen-doped graphene, average grain diameter is about 5.4nm, under discharge current density 0.1A/g, the reversible specific volume after cycle 100 times
Amount is about 1268mAh/g, and capacity retention ratio is up to 93.6%.
Embodiment 7
1. preparing
S1. under the conditions of magnetic agitation, 8ml cyanamide aqueous solutions is added dropwise into 100mg graphene oxide water solutions, wait disperseing
It after uniformly, is transferred in 250ml three-necked flasks, for 24 hours, and continued mechanical stirs 90 DEG C of water-baths, then by being filtered by vacuum, doing
It is dry, obtain nitrogen-doped graphene；
S2. it weighs the stirring of 30mg nitrogen-doped graphenes or ultrasound is dispersed in 185ml acetone, 3.3ml is then added dropwise
0.55mol l-1Dissolved with FeSO4Acetone soln, then 4ml deionized waters are added dropwise, stir after a period of time in 200ml water heating kettles
100 DEG C of hydro-thermal reaction 4h, then through suction filtration, drying, washing, obtain FeO/ nitrogen-doped graphene dusty materials；
S3. by 20ml 4.5mg ml-1Graphene oxide be dispersed in 25ml aqueous solutions, weigh in 472.5mg S2
Product disperses in 20ml ethanol solutions, then the latter's dispersant liquid drop is added in the former dispersion liquid, after being uniformly dispersed, in 50ml
160 DEG C of secondary hydro-thermal reaction 18h in water heating kettle, obtain FeO/ nitrogen-doped graphene hydrogels；
S4. the hydrogel in step S3 is cut into pole piece size, 30 DEG C of natural shrinkages are dried 36h, obtained viscous without addition
Tie the FeO/ nitrogen-doped graphene electrode plates of agent.
2. performance evaluation
After tested, the density of above-mentioned combination electrode is 1.8mg/cm3, FeO nano particle uniform loads in above-mentioned hydrogel
On nitrogen-doped graphene, average grain diameter is about 4.8nm, under discharge current density 0.1A/g, the reversible specific volume after cycle 100 times
Amount is about 814mAh/g, and capacity retention ratio is up to 95.4%.
Embodiment 8
1. preparing
S1. under the conditions of magnetic agitation, 5g aqueous solution of urea is added dropwise into 100mg graphene oxide water solutions, waits for that dispersion is equal
It after even, is transferred in 250ml three-necked flasks, for 24 hours, and continued mechanical stirs 110 DEG C of water-baths, then by being filtered by vacuum, doing
It is dry, obtain nitrogen-doped graphene；
S2. it weighs the stirring of 30mg nitrogen-doped graphenes or ultrasound is dispersed in 185ml absolute ethyl alcohols, be then added dropwise
3ml 0.58mol l-1Dissolved with SnCl4Ethanol solution, then 4ml deionized waters are added dropwise, stir after a period of time in 200ml
110 DEG C of hydro-thermal reaction 5h in water heating kettle, then through suction filtration, drying, washing, obtain SnO2/ nitrogen-doped graphene dusty material；
S3. by 35ml 4.1mg ml-1Graphene oxide be dispersed in 25ml aqueous solutions, weigh the production in 813mg S2
Object disperses in 20ml ethanol solutions, then the latter's dispersant liquid drop is added in the former dispersion liquid, after being uniformly dispersed, in 50ml water
190 DEG C of secondary hydro-thermal reactions for 24 hours, obtain SnO in hot kettle2/ nitrogen-doped graphene hydrogel；
S4. the hydrogel in step S3 is cut into pole piece size, 35 DEG C of natural shrinkages are dried 40h, obtained viscous without addition
Tie the high density SnO of agent2/ nitrogen-doped graphene composite electrode pole piece.
2. performance evaluation
After tested, the density of above-mentioned combination electrode is 2.0mg/cm3, SnO in above-mentioned hydrogel2Nano particle uniform load
On nitrogen-doped graphene, average grain diameter is about 5.7nm, under discharge current density 0.1A/g, the reversible specific volume after cycle 100 times
Amount is about 859mAh/g, and capacity retention ratio is up to 98.9%.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitute, combination and simplify,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. a kind of highdensity metal oxide of self-supporting/nitrogen-doped graphene combination electrode, which is characterized in that the compound electric
Pole is to obtain nitrogen-doped graphene by water-bath first, then in organic solvent by nitrogen-doped graphene dispersion, be added dropwise molten
The organic solvent for having metal salt carries out hydro-thermal reaction I after being uniformly dispersed, powdery metal oxide/nitrogen-doped graphene is made
Composite material；Small amounts graphene solution is added, makes metal oxide/nitrogen-doped graphene composite material in graphite oxide
It is uniformly dispersed in alkene, metal oxide/nitrogen-doped graphene hydrogel is made by secondary hydro-thermal reaction II, finally by cutting
Piece, natural shrinkage drying are made.
2. the highdensity metal oxide of self-supporting/nitrogen-doped graphene combination electrode according to claim 1, feature
It is, the solution concentration of the metal salt is 0.01~0.8mol/L；The mole of the metal salt and graphene oxide
Mass ratio is (0.01~0.1) mol：1g, a concentration of 1.5~3mg/ml of the graphene oxide solution.
3. the highdensity metal oxide of self-supporting/nitrogen-doped graphene combination electrode according to claim 1, feature
It is, the organic solvent is absolute ethyl alcohol, acetone, ether or isopropanol.
4. the highdensity metal oxide of self-supporting/nitrogen-doped graphene combination electrode according to claim 1, feature
It is, the metal salt is titanium salt, pink salt, antimonic salt or molysite.
5. the highdensity metal oxide of self-supporting/nitrogen-doped graphene combination electrode according to claim 4, feature
It is, the titanium salt is one or more of titanium tetrachloride, phthalic acid or Titanium Nitrate；The pink salt is stannic chloride, chlorination
One or more of stannous, nitric acid tin, STANNOUS SULPHATE CRYSTALLINE or nitric acid stannous；The antimonic salt is in antimony chloride, antimony sulfate or sour antimony
More than one；The molysite is one or more of iron chloride, ferric nitrate, ferrous sulfate or ferrous nitrate.
6. the highdensity metal oxide of self-supporting/nitrogen-doped graphene combination electrode according to claim 1, feature
It is, the temperature of the water-bath is 90~120 DEG C；The temperature of the hydro-thermal reaction I is 100~130 DEG C, and the hydro-thermal is anti-
The time for answering I is 0.5~8h；The temperature of the hydro-thermal reaction II is 160~220 DEG C, time of the hydro-thermal reaction II is 6~
24h。
7. according to the highdensity metal oxide of claim 1-6 any one of them self-supportings/nitrogen-doped graphene compound electric
The preparation method of pole, which is characterized in that comprise the following specific steps that：
S1. under the conditions of magnetic agitation, rich nitrogen reagent aqueous solution is added dropwise into graphene oxide water solution, after being uniformly dispersed, into
Row water-bath, and continue to stir, then by filtering, drying, obtain nitrogen-doped graphene
S2. nitrogen-doped graphene is evenly dispersed in organic solvent, then successively be added dropwise dissolved with metal salt organic solvent and
Deionized water carries out hydro-thermal reaction I after stirring a period of time in water heating kettle, then through suction filtration, drying, washing, obtains metal oxygen
Compound/nitrogen-doped graphene powder；
S3. graphene oxide dispersion is formed into dispersion liquid A, step S2 gained metal oxide/N doping graphite in aqueous solution
Alkene powder is dispersed in formation dispersion liquid B in ethanol solution, then dispersion liquid B is added dropwise in dispersion liquid A, after being uniformly dispersed,
Secondary hydro-thermal reaction II is carried out in water heating kettle, obtains metal oxide/nitrogen-doped graphene hydrogel；
S4. hydrogel obtained by step S3 is cut into electrode slice, natural shrinkage drying, obtain the highdensity golden oxide of self-supporting/
Nitrogen-doped graphene combination electrode.
8. the highdensity metal oxide of self-supporting/nitrogen-doped graphene combination electrode according to claim 7, feature
It is, the rich nitrogen reagent in step S1 is one kind or arbitrary in cyanamide, triethylamine, urea, azodiisobutyronitrile or aniline
Two kinds, the time of the water-bath is 6~36h；Metal in metal oxide described in step S2/nitrogen-doped graphene powder
The average grain diameter of oxide is 2~6nm.
9. the highdensity metal oxide of self-supporting/nitrogen-doped graphene combination electrode according to claim 7, feature
Be, graphene oxide described in step S3 be hydrogel gross mass 15~20wt%, graphene oxide a concentration of 1.5~
3mg/ml；Dry temperature described in step S4 is 20~40 DEG C, and the time of the drying is 12~60h.
10. the highdensity metal oxide of claim 1-6 any one of them self-supportings/nitrogen-doped graphene combination electrode exists
Application in lithium ion battery or sodium-ion battery field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810301529.5A CN108630918B (en) | 2018-04-04 | 2018-04-04 | Self-supporting high-density metal oxide/nitrogen-doped graphene composite electrode and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810301529.5A CN108630918B (en) | 2018-04-04 | 2018-04-04 | Self-supporting high-density metal oxide/nitrogen-doped graphene composite electrode and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108630918A true CN108630918A (en) | 2018-10-09 |
| CN108630918B CN108630918B (en) | 2021-04-06 |
Family
ID=63704739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810301529.5A Active CN108630918B (en) | 2018-04-04 | 2018-04-04 | Self-supporting high-density metal oxide/nitrogen-doped graphene composite electrode and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108630918B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109970155A (en) * | 2019-01-28 | 2019-07-05 | 中南大学 | A kind of preparation method of graphene oxide modification lead dioxide electrode |
| CN110190256A (en) * | 2019-05-23 | 2019-08-30 | 广东工业大学 | A kind of antimony oxide/nitrogen-doped graphene composite material and preparation method and application |
| CN111463412A (en) * | 2020-03-10 | 2020-07-28 | 广东省石油与精细化工研究院 | Vanadium pentoxide @ graphene composite electrode material and preparation method thereof |
| CN111686688A (en) * | 2020-06-23 | 2020-09-22 | 广东工业大学 | Amino-modified graphene hydrogel and preparation method and application thereof |
| CN111933893A (en) * | 2020-07-27 | 2020-11-13 | 西北工业大学 | Flexible reduced graphene oxide coated tin phosphide film sodium metal battery cathode and preparation method thereof |
| CN114162808A (en) * | 2021-12-03 | 2022-03-11 | 北京蒙京石墨新材料科技研究院有限公司 | Nitrogen-doped graphene and preparation method and application thereof |
| CN115043463A (en) * | 2022-06-20 | 2022-09-13 | 南通科顺建筑新材料有限公司 | Bimetal-graphene composite electrode, preparation method and water treatment device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159228A (en) * | 2016-07-26 | 2016-11-23 | 广东工业大学 | A kind of nitrogen-doped graphene metal oxide nano composite material and its preparation method and application |
| CN106997954A (en) * | 2017-06-13 | 2017-08-01 | 沈阳建筑大学 | A kind of preparation method of nitrogen-doped graphene/di-iron trioxide combination electrode material |
| CN107578929A (en) * | 2017-08-22 | 2018-01-12 | 哈尔滨工程大学 | Preparation method for the difunctional hydrogel anode material of the controlled shape in mixed biologic power supply |
-
2018
- 2018-04-04 CN CN201810301529.5A patent/CN108630918B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159228A (en) * | 2016-07-26 | 2016-11-23 | 广东工业大学 | A kind of nitrogen-doped graphene metal oxide nano composite material and its preparation method and application |
| CN106997954A (en) * | 2017-06-13 | 2017-08-01 | 沈阳建筑大学 | A kind of preparation method of nitrogen-doped graphene/di-iron trioxide combination electrode material |
| CN107578929A (en) * | 2017-08-22 | 2018-01-12 | 哈尔滨工程大学 | Preparation method for the difunctional hydrogel anode material of the controlled shape in mixed biologic power supply |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109970155A (en) * | 2019-01-28 | 2019-07-05 | 中南大学 | A kind of preparation method of graphene oxide modification lead dioxide electrode |
| CN109970155B (en) * | 2019-01-28 | 2022-01-04 | 中南大学 | Preparation method of lead dioxide electrode modified by graphene oxide |
| CN110190256A (en) * | 2019-05-23 | 2019-08-30 | 广东工业大学 | A kind of antimony oxide/nitrogen-doped graphene composite material and preparation method and application |
| CN111463412A (en) * | 2020-03-10 | 2020-07-28 | 广东省石油与精细化工研究院 | Vanadium pentoxide @ graphene composite electrode material and preparation method thereof |
| CN111463412B (en) * | 2020-03-10 | 2021-08-24 | 广东省石油与精细化工研究院 | Vanadium pentoxide @ graphene composite electrode material and preparation method thereof |
| CN111686688A (en) * | 2020-06-23 | 2020-09-22 | 广东工业大学 | Amino-modified graphene hydrogel and preparation method and application thereof |
| CN111686688B (en) * | 2020-06-23 | 2022-06-24 | 广东工业大学 | Amino-modified graphene hydrogel and preparation method and application thereof |
| CN111933893A (en) * | 2020-07-27 | 2020-11-13 | 西北工业大学 | Flexible reduced graphene oxide coated tin phosphide film sodium metal battery cathode and preparation method thereof |
| CN111933893B (en) * | 2020-07-27 | 2023-04-07 | 西北工业大学 | Flexible reduced graphene oxide coated tin phosphide film sodium metal battery cathode and preparation method thereof |
| CN114162808A (en) * | 2021-12-03 | 2022-03-11 | 北京蒙京石墨新材料科技研究院有限公司 | Nitrogen-doped graphene and preparation method and application thereof |
| CN115043463A (en) * | 2022-06-20 | 2022-09-13 | 南通科顺建筑新材料有限公司 | Bimetal-graphene composite electrode, preparation method and water treatment device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108630918B (en) | 2021-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108630918A (en) | A kind of highdensity metal oxide of self-supporting/nitrogen-doped graphene combination electrode and its preparation method and application | |
| Li et al. | Phosphorus doped Co9S8@ CS as an excellent air-electrode catalyst for zinc-air batteries | |
| Spinner et al. | Effect of nickel oxide synthesis conditions on its physical properties and electrocatalytic oxidation of methanol | |
| Yu et al. | FeCo-doped hollow bamboo-like CN composites as cathodic catalysts for zinc-air battery in neutral media | |
| Zhang et al. | Ni (NO3) 2-induced high electrocatalytic hydrogen evolution performance of self-supported fold-like WC coating on carbon fiber paper prepared through molten salt method | |
| Lai et al. | Bimetallic organic framework-derived rich pyridinic N-doped carbon nanotubes as oxygen catalysts for rechargeable Zn-air batteries | |
| Liang et al. | Cubic pyrite nickel sulfide nanospheres decorated with Ketjen black@ sulfur composite for promoting polysulfides redox kinetics in lithium-sulfur batteries | |
| CN108735997A (en) | A kind of LiFePO4 based composites, preparation method and the usage more than LiFePO4 theoretical capacity | |
| Fang et al. | Fe0. 96S/Co8FeS8 nanoparticles co-embedded in porous N, S codoped carbon with enhanced bifunctional electrocatalystic activities for all-solid-state Zn-air batteries | |
| CN108711611A (en) | A kind of metal nanoparticle/graphene of three-dimensional high-density is composite porous and its preparation method and application | |
| CN106450249A (en) | Bismuth/nickel hydroxide secondary alkaline battery and preparation method thereof | |
| CN104868094A (en) | Porous ruthenium dioxide and manganese dioxide combined electrode and preparation method and application thereof | |
| CN110085440A (en) | A kind of nickel hydroxide/redox graphene electrode material preparation method | |
| CN106298263A (en) | A kind of bismuth/charcoal super capacitance cell and preparation method thereof | |
| CN106784896A (en) | The zinc-air battery transition metal oxide high dispersive porous C catalyst of doping | |
| Liu et al. | Effect of mesoporous α-Fe2O3 nanoparticles doping on the structure and electrochemical hydrogen storage properties of Co0. 9Cu0. 1Si alloy | |
| CN109768260A (en) | A kind of two cobalts of phosphatization/carbon composite and its preparation method and application | |
| Wang et al. | Core-shell MOF-derived Fe3C-Co-NC as high-performance ORR/OER bifunctional catalyst | |
| CN105702958A (en) | SnO2 quantum dot solution and preparation method and application of composite material thereof | |
| CN111634954A (en) | Iron-modified cobalt-iron oxide with self-assembled flower ball structure and preparation and application thereof | |
| Yu et al. | One-step construction of Ni/Co-doped C–N nanotube composites as excellent cathode catalysts for neutral zinc–air battery | |
| CN108428562A (en) | A kind of composite material and its two-step synthesis method of ternary cobalt nickel molybdenum oxide growth in situ on graphene | |
| Chang et al. | Influence of preparation conditions of spherical nickel hydroxide on its electrochemical properties | |
| Liu et al. | Synergic adsorption and catalytic conversion of polysulfides based on polar Mo2C and pyridinic N for the enhanced electrochemical performance of Li–S batteries | |
| CN110586127A (en) | Preparation method and application of platinum-cobalt bimetallic hollow nanospheres |
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 |