CN106531988A - N-doped carbon self-cladding semiconductor metal oxide and graphene composite electrode material and preparation method thereof - Google Patents
N-doped carbon self-cladding semiconductor metal oxide and graphene composite electrode material and preparation method thereof Download PDFInfo
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Abstract
An N-doped carbon self-cladding semiconductor metal oxide and graphene composite electrode material and a preparation method thereof belong to the field of lithium ion battery technology. The material can be applied in the field of energy, especially in the field of power supply lithium ion battery. By a solvothermal method, a compound of an organometallic compound and graphene is firstly obtained; and then in the atmosphere of ammonia gas, heat treatment is carried out to obtain an N-doped carbon self-cladding semiconductor metal oxide and graphene composite electrode material. The synthetic method is simple and feasible. More important, there is no need to additionally add other carbon sources during the whole synthetic process. The organic part in a metal organic precursor directly undergoes thermal decomposition and carbonization to be self-cladded on the surface of metal oxide nanoparticles. In addition, the metal oxide nanoparticles are obtained by converting the metal part in the precursor through thermal decomposition. The whole chemical change process is accompanied with doping of nitrogen.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to the carbon that a kind of nitrogen is adulterated entirely coats semiconductor alloy certainly
Oxide and graphene combination electrode material and preparation method thereof.The material can be in energy field, particularly in electrical source of power
It is applied in field of lithium ion battery.
Background technology
Lithium rechargeable battery as a kind of equipment of energy stores by people's extensive concern, due to its have it is many excellent
Different characteristic, such as energy density are high, have extended cycle life, light weight and self-discharge phenomenon are little etc..At present, used by business
Negative material is mainly based on graphite, although its advantage of lower cost, but very low (the 372mAh g of its theoretical capacity-1) and
Its application is limited with security performance also very low problem.Metal oxide semiconductor material have have extended cycle life,
The features such as theoretical specific capacity height and safety and environmental protection, compared with material with carbon element, metal oxide semiconductor also has intercalation potential height, changes
Learn the advantages such as good stability.But the defect that the electronic conductivity of metal oxide semiconductor material itself is low significantly limit
Its application.
At present, the method which is modified is had：Design synthesis nanostructured, doping, carbon coating and with high conductivity
Material is combined.Design synthesizes nanostructured, and the structure can reduce the transmission path of lithium ion and electronics, and then can be with
Promote dynamic performance of the material under the conditions of lithium battery high power charging-discharging.In addition, pass through theoretical calculation and experiment all prove,
Doping can also improve the electric conductivity of semi-conducting material to a certain extent.Carbon coating is that a kind of relatively conventional raising material is led
Electrical method, it not only can improve the electric conductivity of material, and it is swollen in the volume that process of intercalation causes to limit material
It is swollen, and then improve the chemical property of material.Such as, Chinese patent CN103274453A disclose it is a kind of first by titanium dioxide and
Ionic liquid mix, after through calcining obtain carbon-nitrogen doped titanium dioxide, then the nitrogen for having prepared carbon coating as raw material
The lithium titanate composite material of doping.The material shows excellent electrochemical lithium storage performance.Et al. synthesize the carbon of N doping
The Li of cladding4Ti5O12Nano-complex, shows high high rate performance (Zhang YQ, Du F, Yan X, Jin YM, Zhu
K,Wang X,Li HM,Chen G,Wang CZ,Wei YJ,ACS Appl Mater Interfaces 2014；6:4458-
4465.).Besides it is combined with the material of high conductivity, it is also possible to improve the electric conductivity of semi-conducting material.Graphene is one
The carbon monoatomic layer structure of kind of two dimension, due to ultra-thin thickness, larger specific surface area, the advantages of high conductance,
Make which be widely used in fields such as electronic technology, energy storages, therefore can be combined as a kind of conductive agent.Yan
Et al. report TiO2(B) graphene composite material with N doping, also shows outstanding chemical property (Yan X, Li
YJ,Li ML,Jin YC,Du F,Chen G,Wei YJ,J Mater Chem A 2015；3:4180-4187.).
Up to the present, these strategies for improving material are mostly that one or two strategies are modified to material, are not also had
Being had a kind of material is carried out various strategies while modifying to improve material electrochemical performance.For this purpose, we have proposed a kind of simple
Method, i.e. one-step synthesis goes out the carbon of the full doping of nitrogen { i.e. (carbon of N doping) is from wrapping from the semi-conducting material for coating and Graphene
(semi-conducting material of N doping) and the Graphene of N doping for covering } combination electrode material.The material is specially with N doping
Carbon is further combined with the Graphene of N doping come the conductor oxidate for coating N doping.
The content of the invention
It is an object of the invention to provide the carbon that a kind of nitrogen is adulterated entirely is combined from metal oxide semiconductor is coated with Graphene
Electrode material and preparation method thereof.
The present invention first obtains the compound of organo-metallic compound and Graphene using the method for solvent heat, then in ammonia
The carbon of the full doping of nitrogen is thermally treated resulting in the atmosphere of presence from cladding metal oxide semiconductor and graphene combination electrode material.Should
Synthetic method is simple, and more importantly need not additionally add other carbon sources in whole building-up process, is had by metal
Organic moiety in machine presoma directly thermally decomposes the surface that carbonization is coated on metal oxide nanoparticles certainly, in addition metal oxygen
Compound nano-particle is transformed by the thermal decomposition of metal part in presoma, is accompanied by whole chemical change process
The doping of nitrogen.
The carbon that nitrogen of the present invention is adulterated entirely is from cladding metal oxide semiconductor and graphene combination electrode material
Preparation method, step are following (all raw materials can be obtained from conven-tional channels)：
(1) 20-100 milligrams graphene oxide was obtained in 15-40 milliliter organic solvent for ultrasonic dispersion 30-120 minutes
Graphene oxide dispersion；
(2) 5-15 milliliters same step (1) identical organic solvent and 5-20 milliliters glycerine are mixed, 15-60 point of stirring
Clock, makes uniform mixed solution；
(3) 0.4-2.0 gram of slaine is added in the solution of step (2), stirs 10-60 minutes；
(4) graphene oxide dispersion rapid dumps prepared by step (1) are added in the solution of step (3), are stirred
10-60 minutes；
(5) solution that obtains step (4) loads in reactor, it is closed after thermostatic crystallization at autogenous pressures, treat crystallization
Reactant liquor is centrifuged after finishing, solid product is multiple with absolute ethyl alcohol supersound washing, then in 60～120 DEG C of air dryings 12
～48 hours, organo-metallic compound is obtained with graphene composite material original powder；
(6) by above-mentioned former powder roasting in the mixed atmosphere of nitrogen and ammonia, the carbon for obtaining the full doping of nitrogen is partly led from cladding
Body metal oxide and graphene combination electrode material.
Organic solvent in step (1) and (2) described above is the one kind in methyl alcohol, ethanol, isopropanol or normal propyl alcohol
Or various mixing；
Slaine in step (3) is butyl titanate, titanium tetraisopropylate, titanium tetrachloride, manganese acetate, manganese chloride, acetic acid
In nickel, nickel chloride, nickel sulfate, copper acetate, copper chloride, copper sulphate, copper nitrate, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride
One or more of mixing；
In step (2), step (3) and step (4), the rotating speed of stirring is 500～900 revs/min；
The crystallization temperature of step (5) is 100～140 DEG C, and crystallization time is 36～54 hours；
In step (6) in the mixed atmosphere of nitrogen and ammonia, the volume fraction of ammonia is 5～10%；
In step (6), the temperature of roasting is 450～550 DEG C, and roasting time is 2～10 hours.
Described metal oxide semiconductor include titanium dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, cobaltosic oxide,
Nickel oxide, zinc oxide, cupric oxide, cobalt acid zinc, cobalt acid copper, cobalt acid nickel and cobalt acid manganese etc., such as synthesized using this method other
The metal oxide semiconductor material of metallic element falls within protection scope of the present invention.
Description of the drawings
Fig. 1 is the composite wood of the titanium dioxide that the carbon that the nitrogen of the preparation of the embodiment of the present invention 2 is adulterated entirely is coated certainly and Graphene
X-ray diffraction (XRD) spectrogram of material.
Fig. 2 is the composite that the embodiment of the present invention 2 prepares titanium dioxide of the carbon of the full doping of nitrogen from cladding and Graphene
Scanning figure (figure a), and the distribution map (figure b) of pattern correspondence oxygen element, nitrogen, titanium elements and the carbon.
Fig. 3 prepares the carbon of the full doping of nitrogen from the titanium dioxide and graphene composite material work for coating for the embodiment of the present invention 2
For the high rate performance of cathode of lithium battery.
Specific embodiment
As metal oxide semiconductor material according to the present invention is more, coated with the full doped carbon of synthetic nitrogen certainly below
Titanic oxide material is described in detail the present invention with the composite of Graphene by embodiment, but is not only limited in these examples.
Embodiment 1
(1) by 20 milligrams of graphene oxide ultrasonic disperses in 15 ml methanols, ultrasonically treated graphene oxide 30 minutes,
Obtain graphene oxide solution A liquid；
(2) 10 milliliters of glycerine and 5 ml methanols are mixed, mixing speed is 500 revs/min, stirs 20 minutes, obtains
Solution B liquid；
(3) 0.4g titanium tetrachlorides are added in B liquid, mixing speed is 500 revs/min, is stirred 60 minutes；
(4), in step (3) solution A liquid being all quickly poured under stirring, mixing speed is 700 revs/min,
Stirring 10 minutes；
(5) solution that obtains step (4) loads in reactor, it is closed after crystallization 48 is little at 110 DEG C at autogenous pressures
When, reactant liquor being centrifuged after crystallization is finished, solid product is multiple with absolute ethanol washing, then little in 80 DEG C of air dryings 24
When, obtain the composite of organic titanic compound and Graphene；
(6) by the 450 DEG C of roastings 10 in the mixed atmosphere of nitrogen and ammonia (ammonia volume fraction is 10%) of above-mentioned former powder
Hour, (carbon of N doping) is obtained from (titanium dioxide of N doping) for coating and the composite of the Graphene of N doping, produce
Amount of substance is 0.25g.Characterized by XRD and find that the structure of obtained sample is Anatase (PDF 21-1272), by unit
Element distribution scanned picture understands that oxygen element, nitrogen, titanium elements and carbon are evenly distributed on whole sample topography, from
And show the carbon coating of N doping on the surface of titanium dioxide nanostructure.
Embodiment 2
(1) by 20 milligrams of graphene oxide ultrasonic disperses in 15 milliliters of ethanol, 120 points of ultrasonically treated graphene oxide
Clock, obtains graphene oxide solution A liquid；
(2) by 10 milliliters of glycerine and 5 milliliters of ethanol mixing, mixing speed is 500 revs/min, stirs 60 minutes, obtains
Solution B liquid；
(3) 0.4 gram of titanium tetrachloride is added in B liquid, mixing speed is 600 revs/min, is stirred 30 minutes；
(4), in step (3) solution A liquid being all quickly poured under stirring, mixing speed is 800 revs/min,
Stirring 30 minutes；
(5) aforesaid liquid is loaded in reactor, it is closed after crystallization 48 hours at 110 DEG C at autogenous pressures, treat crystallization
Reactant liquor is centrifuged after finishing, solid product absolute ethanol washing repeatedly, then in 60 DEG C of air dryings 48 hours, is had
The composite of machine titanium compound and Graphene；
(6) by above-mentioned former powder, in the mixed atmosphere of nitrogen and ammonia (ammonia volume fraction is 10%), 500 DEG C of roastings 2 are little
When, (carbon of N doping) is obtained from the composite of the Graphene of (titanium dioxide of N doping) and N doping for coating, product
Quality is 0.26g.Characterized by XRD and find that the structure of obtained sample is Anatase (PDF 21-1272), by element
Distribution scanned picture understands that oxygen element, nitrogen, titanium elements and carbon are evenly distributed on whole sample topography, while
May certify that the carbon coating of N doping on the surface of titanium dioxide nanostructure.
Embodiment 3
(1) by 50 milligrams of graphene oxide ultrasonic disperses in 40 milliliters of ethanol, ultrasonically treated graphene oxide 90 minutes,
Obtain graphene oxide solution A liquid；
(2) by 20 milliliters of glycerine and 10 milliliters of ethanol mixing, mixing speed is 700 revs/min, stirs 15 minutes, obtains
To solution B liquid；
(3) 1.0 grams of titanium tetrachlorides are added in B liquid, mixing speed is 800 revs/min, is stirred 10 minutes；
(4), in step (3) solution A liquid being all quickly poured under stirring, mixing speed is 500 revs/min,
Stirring 60 minutes；
(5) aforesaid liquid is loaded in reactor, it is closed after crystallization 36 hours at 140 DEG C at autogenous pressures, treat crystallization
Reactant liquor is centrifuged after finishing, solid product absolute ethanol washing repeatedly, then in 120 DEG C of air dryings 12 hours, is obtained
The composite of organic titanic compound and Graphene；
(6) by above-mentioned former powder, in the mixed atmosphere of nitrogen and ammonia (ammonia volume fraction is 10%), 550 DEG C of roastings 2 are little
When, (carbon of N doping) is obtained from the composite of the Graphene of (titanium dioxide of N doping) and N doping for coating, product
Quality is 0.65g.Characterized by XRD and find that the structure of obtained sample is Anatase (PDF 21-1272), by element
Distribution scanned picture understands that oxygen element, nitrogen, titanium elements and carbon are evenly distributed on whole sample topography, while
May certify that the carbon coating of N doping on the surface of titanium dioxide nanostructure.
Embodiment 4
(1) by 100 milligrams of graphene oxide ultrasonic disperses in 35 milliliters of ethanol, 60 points of ultrasonically treated graphene oxide
Clock, obtains graphene oxide solution A liquid；
(2) by 20 milliliters of glycerine and 15 milliliters of ethanol mixing, mixing speed is 900 revs/min, stirs 30 minutes, obtains
To solution B liquid；
(3) 2.0 grams of titanium tetrachlorides are added in B liquid, mixing speed is 500 revs/min, is stirred 10 minutes；
(4), in step (3) solution A liquid being all quickly poured under stirring, mixing speed is 700 revs/min,
Stirring 60 minutes；
(5) aforesaid liquid is loaded in reactor, it is closed after crystallization 48 hours at 110 DEG C at autogenous pressures, treat crystallization
Reactant liquor is centrifuged after finishing, solid product absolute ethanol washing repeatedly, then in 80 DEG C of air dryings 1 day, obtains organic
The composite of titanium compound and Graphene；
(6) by above-mentioned former powder, in the mixed atmosphere of nitrogen and ammonia (ammonia volume fraction is 5%), 450 DEG C of roastings 10 are little
When, (carbon of N doping) is obtained from the composite of the Graphene of (titanium dioxide of N doping) and N doping for coating, product
Quality is 1.23g.Characterized by XRD and find that the structure of obtained sample is Anatase (PDF 21-1272), by element
Distribution scanned picture understands that oxygen element, nitrogen, titanium elements and carbon are evenly distributed on whole sample topography, while
May certify that the carbon coating of N doping on the surface of titanium dioxide nanostructure.
Embodiment 5
(1) by 30 milligrams of graphene oxide ultrasonic disperses in 20 milliliters of ethanol, 120 points of ultrasonically treated graphene oxide
Clock, obtains graphene oxide solution A liquid；
(2) by 15 milliliters of glycerine and 15 milliliters of ethanol mixing, mixing speed is 500 revs/min, stirs 60 minutes, obtains
To solution B liquid；
(3) 0.5 gram of titanium tetrachloride is added in B liquid, mixing speed is 700 revs/min, is stirred 30 minutes；
(4), in step (3) solution A liquid being all quickly poured under stirring, mixing speed is 900 revs/min,
Stirring 30 minutes；
(5) aforesaid liquid is loaded in reactor, it is closed after crystallization 48 hours at 120 DEG C at autogenous pressures, treat crystallization
Reactant liquor is centrifuged after finishing, solid product absolute ethanol washing repeatedly, then in 100 DEG C of air dryings 24 hours, is obtained
The composite of organic titanic compound and Graphene；
(6) by above-mentioned former powder, in the mixed atmosphere of nitrogen and ammonia (ammonia volume fraction is 10%), 500 DEG C of roastings 2 are little
When, (carbon of N doping) is obtained from the composite of the Graphene of (titanium dioxide of N doping) and N doping for coating, product
Quality is 0.31g.Characterized by XRD and find that the structure of obtained sample is Anatase (PDF 21-1272), by element
Distribution scanned picture understands that oxygen element, nitrogen, titanium elements and carbon are evenly distributed on whole sample topography, while
May certify that the carbon coating of N doping on the surface of titanium dioxide nanostructure.
Embodiment 6
(1) by 30 milligrams of graphene oxide ultrasonic disperses in 20 milliliters of isopropanols, 120 points of ultrasonically treated graphene oxide
Clock, obtains graphene oxide solution A liquid；
(2) by 15 milliliters of glycerine and 15 milliliters of isopropanol mixing, mixing speed is 900 revs/min, is stirred 60 minutes,
Obtain solution B liquid；
(3) 0.5 gram of titanium tetrachloride is added in B liquid, mixing speed is 900 revs/min, is stirred 30 minutes；
(4), in step (3) solution A liquid being all quickly poured under stirring, mixing speed is 500 revs/min,
Stirring 30 minutes；
(5) aforesaid liquid is loaded in reactor, it is closed after crystallization 48 hours at 110 DEG C at autogenous pressures, treat crystallization
Reactant liquor is centrifuged after finishing, solid product absolute ethanol washing repeatedly, then in 80 DEG C of air dryings 1 day, obtains organic
The composite of titanium compound and Graphene；
(6) by above-mentioned former powder, in the mixed atmosphere of nitrogen and ammonia (ammonia volume fraction is 10%), 500 DEG C of roastings 2 are little
When, (carbon of N doping) is obtained from the composite of the Graphene of (titanium dioxide of N doping) and N doping for coating, product
Quality is 0.29g.Characterized by XRD and find that the structure of obtained sample is Anatase (PDF 21-1272), by element
Distribution scanned picture understands that oxygen element, nitrogen, titanium elements and carbon are evenly distributed on whole sample topography, while
May certify that the carbon coating of N doping on the surface of titanium dioxide nanostructure.
The carbon that nitrogen of the present invention is adulterated entirely is from cladding metal oxide semiconductor material and graphene composite material
Performance of lithium ion battery tests (preparation of electrode and test condition)：
The carbon that the nitrogen that above-described embodiment 2 is obtained is adulterated entirely is combined from metal oxide semiconductor material is coated with Graphene
Used as active material, acetylene black is conductive agent to material, and polytetrafluoroethylene (PTFE) is binding agent, is 80 in mass ratio by which：10：10 ratio
Example, with METHYLPYRROLIDONE as solvent, mixing is coated in copper foil current collector the negative pole as battery, and positive pole is used
Elemental lithium paper tinsel, adds electrolyte to be assembled into battery, carries out charge-discharge test, discharge and recharge 3～0.01V of window with battery test system
(vs Li/Li+).As shown in figure 3, the high rate performance of 2 obtained sample of embodiment is：100,200,400,800,1000,
2000 and 3000mAg-1Under current density after 10 circle of circulation, the specific capacity for obtaining is 298,236,203,168,164,128 Hes
115mAh g-1, the material shows outstanding chemical property.
Claims (9)
1. the carbon that a kind of nitrogen is adulterated entirely coats the preparation method of metal oxide semiconductor and graphene combination electrode material certainly, its
Step is as follows：
(1) 20-100 milligrams graphene oxide was aoxidized in 15-40 milliliter organic solvent for ultrasonic dispersion 30-120 minutes
Graphene dispersing solution；
(2) 5-15 milliliters same step (1) identical organic solvent and 5-20 milliliters glycerine are mixed, is stirred 15-60 minutes, system
Uniformly mixed solution；
(3) 0.4-2.0 gram of slaine is added in the solution of step (2), stirs 10-60 minutes；
(4) graphene oxide dispersion rapid dumps prepared by step (1) are added in the solution of step (3), stir 10-60
Minute；
(5) solution that obtains step (4) loads in reactor, it is closed after thermostatic crystallization at autogenous pressures, treat that crystallization is finished
Afterwards reactant liquor is centrifuged, solid product is multiple with absolute ethyl alcohol supersound washing, then in 60～120 DEG C of air dryings 12～48
Hour, organo-metallic compound is obtained with graphene composite material original powder；
(6) by above-mentioned former powder roasting in the mixed atmosphere of nitrogen and ammonia, the carbon for obtaining the full doping of nitrogen is golden from semiconductor is coated
Category oxide and graphene combination electrode material.
2. the carbon that a kind of nitrogen as claimed in claim 1 is adulterated entirely is from cladding metal oxide semiconductor and graphene combination electrode
The preparation method of material, it is characterised in that：Organic solvent in step (1) and (2) is methyl alcohol, ethanol, isopropanol or normal propyl alcohol
In one or more of mixing.
3. the carbon that a kind of nitrogen as claimed in claim 1 is adulterated entirely is from cladding metal oxide semiconductor and graphene combination electrode
The preparation method of material, it is characterised in that：Slaine described in step (3) is butyl titanate, titanium tetraisopropylate, four chlorinations
Titanium, manganese acetate, manganese chloride, nickel acetate, nickel chloride, nickel sulfate, copper acetate, copper chloride, copper sulphate, copper nitrate, zinc acetate, nitric acid
The mixing of one or more in zinc, zinc sulfate, zinc chloride.
4. the carbon that a kind of nitrogen as claimed in claim 1 is adulterated entirely is from cladding metal oxide semiconductor and graphene combination electrode
The preparation method of material, it is characterised in that：In step (2), step (3) and step (4), the rotating speed of stirring is 500～900 revs/min
Clock.
5. the carbon that a kind of nitrogen as claimed in claim 1 is adulterated entirely is from cladding metal oxide semiconductor and graphene combination electrode
The preparation method of material, it is characterised in that：The crystallization temperature of step (5) is 100～140 DEG C, and crystallization time is 36～54 hours.
6. the carbon that a kind of nitrogen as claimed in claim 1 is adulterated entirely is from cladding metal oxide semiconductor and graphene combination electrode
The preparation method of material, it is characterised in that：In step (6) in the mixed atmosphere of nitrogen and ammonia, the volume fraction of ammonia is 5～
10%.
7. the carbon that a kind of nitrogen as claimed in claim 1 is adulterated entirely is from cladding metal oxide semiconductor and graphene combination electrode
The preparation method of material, it is characterised in that：In step (6), the temperature of roasting is 450～550 DEG C, and roasting time is 2～10 little
When.
8. the carbon that a kind of nitrogen as claimed in claim 1 is adulterated entirely is from cladding metal oxide semiconductor and graphene combination electrode
The preparation method of material, it is characterised in that：Metal oxide semiconductor be titanium dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, four
Co 3 O, nickel oxide, zinc oxide, cupric oxide, cobalt acid zinc, cobalt acid copper, cobalt acid nickel or cobalt acid manganese.
9. the carbon that a kind of nitrogen is adulterated entirely is from cladding metal oxide semiconductor and graphene combination electrode material, it is characterised in that：
It is to be prepared by claim 1～8 any one method.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107658433A (en) * | 2017-04-17 | 2018-02-02 | 陕西科技大学 | N doping nickel cobalt oxygen nano-wire array and preparation method thereof |
| CN109248712A (en) * | 2017-07-14 | 2019-01-22 | 中国科学院苏州纳米技术与纳米仿生研究所 | Monatomic dopen Nano carbon material catalytic carrier of metal and its preparation method and application |
| CN111129459A (en) * | 2019-12-20 | 2020-05-08 | 佛山科学技术学院 | graphene/Mn3O4Preparation method and application of composite material |
| CN111554517A (en) * | 2020-05-12 | 2020-08-18 | 邓李金 | Nitrogen-doped porous carbon-coated nano NiCo2O4Electrode active material and method for producing the same |
| CN113201749A (en) * | 2021-03-30 | 2021-08-03 | 广州费舍尔人工智能技术有限公司 | Sulfur-doped copper cobaltate modified carbon nanotube bifunctional electrode catalyst |
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| CN104868112A (en) * | 2015-05-12 | 2015-08-26 | 吉林大学 | Carbon-coated titanium dioxide nanosheet array and graphene composite electrode material and preparation method thereof |
| CN105390677A (en) * | 2015-11-02 | 2016-03-09 | 吉林大学 | Carbon self-coated semiconductor metal oxide nanosheet and graphene composite material and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104868112A (en) * | 2015-05-12 | 2015-08-26 | 吉林大学 | Carbon-coated titanium dioxide nanosheet array and graphene composite electrode material and preparation method thereof |
| CN105390677A (en) * | 2015-11-02 | 2016-03-09 | 吉林大学 | Carbon self-coated semiconductor metal oxide nanosheet and graphene composite material and application thereof |
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| CN107658433A (en) * | 2017-04-17 | 2018-02-02 | 陕西科技大学 | N doping nickel cobalt oxygen nano-wire array and preparation method thereof |
| CN109248712A (en) * | 2017-07-14 | 2019-01-22 | 中国科学院苏州纳米技术与纳米仿生研究所 | Monatomic dopen Nano carbon material catalytic carrier of metal and its preparation method and application |
| CN109248712B (en) * | 2017-07-14 | 2021-07-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Metal monoatomic doped nano carbon material catalytic carrier and preparation method and application thereof |
| CN111129459A (en) * | 2019-12-20 | 2020-05-08 | 佛山科学技术学院 | graphene/Mn3O4Preparation method and application of composite material |
| CN111554517A (en) * | 2020-05-12 | 2020-08-18 | 邓李金 | Nitrogen-doped porous carbon-coated nano NiCo2O4Electrode active material and method for producing the same |
| CN113201749A (en) * | 2021-03-30 | 2021-08-03 | 广州费舍尔人工智能技术有限公司 | Sulfur-doped copper cobaltate modified carbon nanotube bifunctional electrode catalyst |
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