CN103647072B - A kind of nickel oxide surfaces carbon/nitrogen content is than the preparation method of adjustable nitrogen-doped carbon integument - Google Patents
A kind of nickel oxide surfaces carbon/nitrogen content is than the preparation method of adjustable nitrogen-doped carbon integument Download PDFInfo
- Publication number
- CN103647072B CN103647072B CN201310723668.4A CN201310723668A CN103647072B CN 103647072 B CN103647072 B CN 103647072B CN 201310723668 A CN201310723668 A CN 201310723668A CN 103647072 B CN103647072 B CN 103647072B
- Authority
- CN
- China
- Prior art keywords
- carbon
- nitrogen
- nickel oxide
- nickel
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- 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
- 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
-
- 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
Abstract
A kind of nickel oxide surfaces carbon/nitrogen content is than the preparation method of adjustable nitrogen-doped carbon integument, with bicarbonate nickel nano particle for presoma, with 1,3-dialkyl group substituted imidazole ionic liquid is covering, 160 ~ 200 ° of C carry out solvent-thermal method process, product, through carbonization, forms carbon/nitrogen than adjustable nitrogen-doped carbon integument at nickel oxide surfaces.Described method is carried out coated by selecting the ionic liquid of different carbon/nitrogen ratio to presoma, after heat treatment can at hollow porous nickel oxide surfaces carbon coated/nitrogen content than adjustable N doping carbon-coating.The invention provides the adjustable method of the carbon/nitrogen content ratio in a kind of simple, effective nitrogen-doped carbon coating layer, N doping carbon-coating is coated on hollow porous nickel oxide nano material surface, significantly improve conductivity and the discharge stability of nickel oxide, be specially adapted to lithium ion secondary electrode anode material; The inventive method is simple, economical, is applicable to industrialization large-scale production.
Description
Technical field
The present invention relates to a kind of preparation method of nickel oxide integument, be specifically related to the preparation method of a kind of nickel oxide surfaces carbon/nitrogen content than adjustable nitrogen-doped carbon integument, carbon/nitrogen prepared by the method can carry out finishing to NiO nanoparticle than adjustable nitrogen-doped carbon integument, the composite material formed, as negative electrode of lithium ionic secondary battery, belongs to materials chemistry and energy battery technical field.
Background technology
Lithium ion battery because of its have that energy density is high, output voltage is high, good cycle, long service life, environmental protection advantageous property, the fields such as portable electronic product, war industry, Aero-Space are widely used in recent years, also have broad prospects in the power set application of following electric automobile (EV) and hybrid-electric car (HEV), therefore improve the focus that performance of lithium ion battery is research at present.Wherein, the selection of electrode material is the key factor of performance of lithium ion battery.
As one of important inorganic material, nickel oxide has the advantages such as nature storage is abundant, cheap, Heat stability is good, is widely used in the numerous areas such as catalysis, gas sensor, magnetic material at present.Nickel oxide has theoretical specific capacity high (718mAh/g), advantages of environment protection as lithium ion battery negative material.Nickel oxide is one of current widely used lithium ion battery negative material of new generation.But because the design feature of nickel oxide self and conventional method such as to prepare at the reason, the problems such as the diffusion rate of lithium ion in nickel oxide particle is very low, battery charging and discharging poor stability.Along with improving constantly battery performance requirements, especially power lithium-ion battery is to the dual high request of energy density and power density, and the lithium ion battery electrode material of development of new, particularly negative material is day by day urgent.
At present, nickel oxide is one of important lithium ion battery negative material.Three-dimensional porous nano-scale hollow ball can shorten ion and electronics migration distance therein effectively, and make electrode material and conductive agent can the mixing of more uniform high-efficiency, thus improve the lithium ion of material internal and the diffusion of electronics and transmission rate, and improve the dynamic characteristic in charge and discharge process.And adopt suitable carbon layer material to carry out finishing to nickel oxide material, be conducive to the utilance and the conductivity that improve nickel oxide further.
Summary of the invention
The object of this invention is to provide a kind of preparation method of carbon/nitrogen content than adjustable nitrogen-doped carbon integument of nickel oxide surfaces, coated with carbon/nitrogen content prepared according to the methods of the invention, than the hollow porous nickel oxide nano material of adjustable N doping carbon-coating, is suitable for lithium ion secondary electrode anode material.
Of the present inventionly be wrapped in the preparation method of the carbon/nitrogen content on hollow porous nickel oxide nano material than adjustable N doping carbon-coating, carbon/nitrogen content is than adjustable, be with different ionic liquids for covering, carbon/nitrogen that formation is wrapped on hollow porous nickel oxide nano material is than adjustable N doping carbon-coating.
The present invention adopts following technical scheme:
A kind of nickel oxide surfaces carbon/nitrogen content is than the preparation method of adjustable nitrogen-doped carbon integument, it is characterized in that, presoma nano nickel bicarbonate is dispersed in covering 1, in 3-dialkyl group substituted imidazole ionic liquid, 160 ~ 200 ° of C carry out solvent-thermal method process, after products therefrom washing, drying, heat-treat under argon gas atmosphere (with 2 ° of C/min temperature programming to 300 ~ 500 ° C), namely form nitrogen-doped carbon integument at nickel oxide nano material surface.
In described method, presoma nano nickel bicarbonate and 1,3-dialkyl group substituted imidazole ionic liquid mol ratio are 1:50 ~ 150.
The described preferred 1-alkyl of 1,3-dialkyl group substituted imidazole salt-3-methyl imidazolium tetrafluoroborate, more preferably, 1-alkyl is wherein C1-C6 alkyl.
In described method, the optimum condition of solvent-thermal method process is 160 ~ 200 ° of C, 3 ~ 5h.
Described presoma nano nickel bicarbonate adopts solvent thermal process preparation, urea, Nickel dichloride hexahydrate, sodium acetate are disperseed in ethylene glycol form mixed liquor, this mixed liquor 160 ~ 200 ° of C are carried out solvent thermal reaction, and namely product obtains bicarbonate nickel nanosphere presoma after washing, drying.
In described mixed liquor, the mol ratio of Nickel dichloride hexahydrate and sodium acetate is 1:3 ~ 5, and Nickel dichloride hexahydrate and urea mol ratio are 1:3.5 ~ 5.5, and the mol ratio of Nickel dichloride hexahydrate and ethylene glycol is 1:95 ~ 100.
In described method, the optimum condition of solvent thermal reaction is 160 ~ 200 ° of C, 18 ~ 24h.
Particularly, the described carbon/nitrogen content being wrapped in hollow porous nickel oxide nano material surface, than the preparation method of adjustable N doping carbon-coating, comprises the steps:
1) in ethylene glycol, add urea, Nickel dichloride hexahydrate and sodium acetate, 3 ~ 5h is stirred at 20 ~ 25 ° of C lower magnetic forces, form finely dispersed mixed liquor, mixed liquor is placed in the stainless steel cauldron of inner liner polytetrafluoroethylene, solvent thermal reaction 18 ~ 24h under 160 ~ 200 ° of C, product is cooled to room temperature, centrifuge washing, under 60 ~ 100 ° of C, dry 12 ~ 24h, obtains presoma bicarbonate nickel nanosphere.
2) 1, products therefrom in step 1) is added in 3-dialkyl group substituted imidazole ionic liquid, ultrasonic disperse is evenly placed in the stainless steel cauldron of inner liner polytetrafluoroethylene, solvent-thermal method process 3 ~ 5h under 160 ~ 200 ° of C, product is cooled to room temperature, after centrifugation under 80 ~ 120 ° of C vacuumize 12 ~ 24h.
3) by step 2) in the desciccate that obtains be placed in tube furnace, heat-treat with 2 ° of C/min temperature programming to 300 ~ 500 ° C under argon gas atmosphere, be cooled to room temperature, namely obtain the N doping carbon-coating being coated on hollow porous nickel oxide nano material surface.
In step 1), in described mixed liquor, the mol ratio of Nickel dichloride hexahydrate and sodium acetate is 1:3 ~ 5, and Nickel dichloride hexahydrate and urea mol ratio are 1:3.5 ~ 5.5, and the mol ratio of Nickel dichloride hexahydrate and ethylene glycol is 1:95 ~ 100.
Step 2) in the consumption of presoma bicarbonate nickel be 30 ~ 80mg, the consumption of ionic liquid is 5 ~ 10mL.
Step 2) ionic liquid used is preferably 1-ethyl-3-methylimidazole tetrafluoroborate ion liquid 1-butyl-3-methyl imidazolium tetrafluoroborate ionic liquid and 1-hexyl-3-methyl imidazolium tetrafluoroborate ionic liquid.
The present invention obtains carbon/nitrogen content than adjustable N doping carbon-coating, can observe it and evenly be coated on hollow porous nickel oxide nano material surface from TEM Electronic Speculum figure (Fig. 1 ~ 3).Carbon/nitrogen content that in XPS spectrum spectrogram, (Fig. 4 ~ 6) visible different ionic liquid covering is formed, than the characteristic peak of carbon, nitrogen element in adjustable N doping carbon-coating, calculates: in three kinds of N doping carbon-coatings, carbon/nitrogen mass ratio is respectively 5:1,7.5:1,10:1.
The inventive method take ionic liquid as covering, carbon/nitrogen that formation is wrapped on hollow porous nickel oxide nano material is than adjustable N doping carbon-coating, compared with conventional solid carbon decorative material, with nitrogen-doped carbon layer material, finishing is carried out to nickel oxide material, be conducive to the conductivity improving nickel oxide, and then improve the utilance of nickel oxide.This can be easy to penetrate in porous material owing to the fluid property that ionic liquid possesses.And, the existence of nitrogen element in carbon-coating, change the Cloud Distribution in carbon-coating around carbon atom, make the carbon-coating of N doping possess more excellent electric conductivity and stable chemical property compared to common carbon-coating, thus improve the conductivity of carbon-coating and the cycle performance of lithium ion battery.In addition by selecting different ionic liquid, can carbon/nitrogen content ratio effectively in control surface carbon decorative layer.Select different ionic liquids and bicarbonate nickel presoma to carry out solvent heat treatment, the hollow porous nickel oxide nano composite material that surface coating layer carbon/nitrogen content is modified than adjustable N doping carbon-coating can be obtained.With this composite material for lithium ion battery negative material prepares lithium ion battery, significantly improve chemical property and the cycle performance of lithium ion battery.
The present invention has following beneficial effect: according to the inventive method, the coated N doping carbon-coating of hollow porous nickel oxide nano material surface has carbon/nitrogen content than adjustability, can by the ratio using different ionic liquids effectively regulate carbon in carbon-coating/nitrogen element.By regulating the ratio of carbon/nitrogen in hollow porous nickel oxide nano material coating layer, improving the conductivity of material further, increasing the chemical property of material.This carbon/nitrogen content is wrapped in hollow porous nickel oxide nano material surface than adjustable N doping carbon-coating and obtains composite material, and this composite material is used for lithium ion battery negative material, thus obtain the lithium ion battery that specific discharge capacity is large, discharge performance good, cyclical stability is high.Carbon/nitrogen content of the present invention is simpler than the preparation method of adjustable N doping carbon-coating effectively, energy-conserving and environment-protective, is easy to promote and large-scale production, significant in high performance lithium ion battery Application and Development field.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not limited with embodiment, but is limited by claim.
Accompanying drawing explanation
Fig. 1 is that embodiment 1 hollow core porous nickel oxide nano-material surface carbon/nitrogen content is than the N doping carbon-coating transmission electron microscope picture being about 5:1.
Fig. 2 is that embodiment 2 hollow core porous nickel oxide nano-material surface carbon/nitrogen content is than the N doping carbon-coating transmission electron microscope picture being about 7.5:1.
Fig. 3 is that embodiment 3 hollow core porous nickel oxide nano-material surface carbon/nitrogen content is than the N doping carbon-coating transmission electron microscope picture being about 10:1.
Fig. 4 is the XPS spectrum figure that embodiment 1 hollow core porous nickel oxide nano-material surface carbon/nitrogen contains than the N doping carbon-coating being about 5:1.
Fig. 5 is the XPS spectrum figure that embodiment 2 hollow core porous nickel oxide nano-material surface carbon/nitrogen contains than the N doping carbon-coating being about 7.5:1.
Fig. 6 is the XPS spectrum figure that embodiment 3 hollow core porous nickel oxide nano-material surface carbon/nitrogen contains than the N doping carbon-coating being about 10:1.
Embodiment
Embodiment 1
In 20mL ethylene glycol, add the Nickel dichloride hexahydrate of 0.895g, the sodium acetate of 1.23g, 1.2g urea respectively, this mixture is placed on magnetic stirring apparatus, under 20 ~ 25 ° of C conditions, stir 3 ~ 5h.Be transferred to after being uniformly dispersed in the stainless steel cauldron of inner liner polytetrafluoroethylene, be placed in baking oven 160 ~ 200 ° of C and heat 18 ~ 24h, reacted rear cool to room temperature.Products therefrom is used respectively ethanol and deionized water centrifuge washing 6 ~ 8 times, and be placed in drying box 60 ~ 100 ° of C vacuumize 12 ~ 24h, obtain presoma bicarbonate nickel nano particle, particle diameter is 200 ~ 300nm about.The presoma of 30mg is joined in the 1-ethyl-3-methylimidazole tetrafluoroborate ion liquid of 5mL, ultrasonic disperse 5 ~ 15min.Scattered solution is placed in again the stainless steel cauldron of inner liner polytetrafluoroethylene, solvent-thermal method process 3 ~ 5h under 160 ~ 200 ° of C, through being cooled to room temperature, the bicarbonate nickel nano particle of ionic liquid after centrifugation, can be enclosed with, by its vacuumize 12 ~ 24h under 80 ~ 120 ° of C.Dried product is placed in tube furnace, heat-treat under argon gas atmosphere (with 2 ° of C/min temperature programming to 300 ~ 500 ° C), namely obtain the N doping carbon-coating on hollow porous nickel oxide composite material surface after being cooled to room temperature, wherein the content mass ratio of carbon and nitrogen element is about 5:1.
Embodiment 2
In 20mL ethylene glycol, add the Nickel dichloride hexahydrate of 0.895g, the sodium acetate of 1.23g, 1.2g urea respectively, this mixture is placed on magnetic stirring apparatus, under 20 ~ 25 ° of C conditions, stir 3 ~ 5h.Be transferred to after being uniformly dispersed in the stainless steel cauldron of inner liner polytetrafluoroethylene, be placed in baking oven 160 ~ 200 ° of C and heat 18 ~ 24h, reacted rear cool to room temperature.Products therefrom is used respectively ethanol and deionized water centrifuge washing 6 ~ 8 times, and be placed in drying box 60 ~ 100 ° of C vacuumize 12 ~ 24h, obtain presoma bicarbonate nickel nano particle, particle diameter is 200 ~ 300nm about.The presoma of 40mg is joined in the 1-butyl-3-methyl imidazolium tetrafluoroborate ionic liquid of 5mL, ultrasonic disperse 5 ~ 15min.Scattered solution is placed in again the stainless steel cauldron of inner liner polytetrafluoroethylene, solvent-thermal method process 3 ~ 5h under 160 ~ 200 ° of C, through being cooled to room temperature, the bicarbonate nickel nano particle of ionic liquid after centrifugation, can be enclosed with, by its vacuumize 12 ~ 24h under 80 ~ 120 ° of C.Dried product is placed in tube furnace, heat-treat under argon gas atmosphere (with 2 ° of C/min temperature programming to 300 ~ 500 ° C), namely obtain the N doping carbon-coating on hollow porous nickel oxide composite material surface after being cooled to room temperature, wherein the content mass ratio of carbon and nitrogen element is about 7.5:1.
Embodiment 3
In 20mL ethylene glycol, add the Nickel dichloride hexahydrate of 0.895g, the sodium acetate of 1.23g, 1.2g urea respectively, this mixture is placed on magnetic stirring apparatus, under 20 ~ 25 ° of C conditions, stir 3 ~ 5h.Be transferred to after being uniformly dispersed in the stainless steel cauldron of inner liner polytetrafluoroethylene, be placed in baking oven 160 ~ 200 ° of C and heat 18 ~ 24h, reacted rear cool to room temperature.Products therefrom is used respectively ethanol and deionized water centrifuge washing 6 ~ 8 times, and be placed in drying box 60 ~ 100 ° of C vacuumize 12 ~ 24h, obtain presoma bicarbonate nickel nano particle, particle diameter is 200 ~ 300nm about.The presoma of 75mg is joined in the 1-hexyl-3-methyl imidazolium tetrafluoroborate ionic liquid of 10mL, ultrasonic disperse 5 ~ 15min.Scattered solution is placed in again the stainless steel cauldron of inner liner polytetrafluoroethylene, solvent-thermal method process 3 ~ 5h under 160 ~ 200 ° of C, through being cooled to room temperature, the bicarbonate nickel nano particle of ionic liquid after centrifugation, can be enclosed with, by its vacuumize 12 ~ 24h under 80 ~ 120 ° of C.Dried product is placed in tube furnace, heat-treat under argon gas atmosphere (with 2 ° of C/min temperature programming to 300 ~ 500 ° C), namely obtain the N doping carbon-coating on hollow porous nickel oxide composite material surface after being cooled to room temperature, wherein the content mass ratio of carbon and nitrogen element is about 10:1.
Comparative example 1
In 20mL ethylene glycol, add the Nickel dichloride hexahydrate of 0.895g, the sodium acetate of 1.23g, 1.2g urea respectively, this mixture is placed on magnetic stirring apparatus, under 20 ~ 25 ° of C conditions, stir 3 ~ 5h.Be transferred to after being uniformly dispersed in the stainless steel cauldron of inner liner polytetrafluoroethylene, be placed in baking oven 160 ~ 200 ° of C and heat 18 ~ 24h, be cooled to room temperature.Product is used respectively ethanol and deionized water centrifuge washing 6 ~ 8 times, and be placed in drying box 60 ~ 100 ° of C vacuumize 12 ~ 24h, obtain presoma bicarbonate nickel nano particle, particle diameter is 200 ~ 300nm about.Join in glucose solution by this presoma, ultrasonic disperse is even.Scattered solution being placed in the stainless steel cauldron of inner liner polytetrafluoroethylene, solvent-thermal method process 3 ~ 5h under 160 ~ 200 ° of C again, through being cooled to room temperature, the bicarbonate nickel nano particle of glucose solution after centrifugation, can being coated with.Its vacuumize 12 ~ 24h under 80 ~ 120 ° of C is placed in tube furnace, heat-treats under argon gas atmosphere (with 2 ° of C/min temperature programming to 300 ~ 500 ° C), after being cooled to room temperature, namely obtain the pure carbon-coating on hollow porous nickel oxide composite material surface.
Comparative example 2
In 20mL ethylene glycol, add the Nickel dichloride hexahydrate of 0.895g, the sodium acetate of 1.23g, 1.2g urea respectively, stir 3 ~ 5h in 20 ~ 25 ° of C lower magnetic forces.Be transferred to after mixing in the stainless steel cauldron of inner liner polytetrafluoroethylene, under 160 ~ 200 ° of C, heated 18 ~ 24h, cool to room temperature.By product respectively after ethanol and deionized water centrifuge washing 6 ~ 8 times, be placed in vacuumize 12 ~ 24h under drying box 60 ~ 100 ° of C, obtain presoma bicarbonate nickel nano particle, particle diameter is 200 ~ 300nm about.This presoma 30mg is added, ultrasonic disperse 5 ~ 15min in the 1-butyl-3-methyl imidazolium tetrafluoroborate ionic liquid of 5mL.Scattered solution is placed in again the stainless steel cauldron of inner liner polytetrafluoroethylene, under 160 ~ 200 ° of C, solvent-thermal method process 6h, is cooled to room temperature, after centrifugation under 80 ~ 120 ° of C vacuumize 12 ~ 24h.Dried product is placed in tube furnace, heat-treats under an argon atmosphere (with 2 ° of C/min temperature programming to 300 ~ 500 ° C), is cooled to room temperature, namely obtains the broken powder nickel oxide material of N doping carbon-coating parcel.
Claims (8)
1. nickel oxide surfaces carbon/nitrogen content is than the preparation method of adjustable nitrogen-doped carbon integument, it is characterized in that, presoma nano nickel bicarbonate is dispersed in covering 1, in 3-dialkyl group substituted imidazole ionic liquid, 160 ~ 200 ° of C carry out solvent-thermal method process 3 ~ 5h, products therefrom, after washing, drying, is heat-treated under argon gas atmosphere, is namely obtained nitrogen-doped carbon integument at nickel oxide nano material surface.
2. preparation method according to claim 1, is characterized in that: described covering 1,3-dialkyl group substituted imidazole ionic liquid is selected from 1-alkyl-3-methyl imidazolium tetrafluoroborate ionic liquid, and 1-alkyl is wherein C1-C6 alkyl.
3. preparation method according to claim 2, is characterized in that: described covering ionic liquid is 1-ethyl-3-methylimidazole tetrafluoroborate ion liquid, 1-butyl-3-methyl imidazolium tetrafluoroborate ionic liquid or 1-hexyl-3-methyl imidazolium tetrafluoroborate ionic liquid.
4. preparation method according to claim 1 and 2, is characterized in that: described presoma nano nickel bicarbonate and 1,3-dialkyl group substituted imidazole ionic liquid mol ratio are 1:50 ~ 150.
5. preparation method according to claim 1 and 2, is characterized in that: described heat treatment method is with 2 ° of C/min temperature programming to 300 ~ 500 ° C.
6. preparation method according to claim 1 and 2, it is characterized in that: described presoma nano nickel bicarbonate adopts solvent thermal process preparation, urea, Nickel dichloride hexahydrate, sodium acetate are disperseed in ethylene glycol form mixed liquor, this mixed liquor 160 ~ 200 ° of C are carried out solvent thermal reaction, and namely product obtains bicarbonate nickel nanosphere presoma after washing, drying.
7. preparation method according to claim 6, it is characterized in that: in described mixed liquor, the mol ratio of Nickel dichloride hexahydrate and sodium acetate is 1:3 ~ 5, Nickel dichloride hexahydrate and urea mol ratio are 1:3.5 ~ 5.5, and the mol ratio of Nickel dichloride hexahydrate and ethylene glycol is 1:95 ~ 100.
8. preparation method according to claim 1, is characterized in that, described method comprises the steps:
1) in ethylene glycol, add urea, Nickel dichloride hexahydrate and sodium acetate, stir 3 ~ 5h in 20 ~ 25 ° of C lower magnetic forces, form finely dispersed mixed liquor; Mixed liquor is placed in the stainless steel cauldron of inner liner polytetrafluoroethylene, solvent thermal reaction 18 ~ 24h under 160 ~ 200 ° of C; Gained product is cooled to room temperature, after centrifuge washing under 60 ~ 100 ° of C dry 12 ~ 24h, obtain presoma bicarbonate nickel nanosphere;
2) in 1,3-dialkyl group substituted imidazole ionic liquid, add products therefrom in step 1), ultrasonic disperse is evenly placed in the stainless steel cauldron of inner liner polytetrafluoroethylene, solvent-thermal method process 3 ~ 5h under 160 ~ 200 ° of C; Product is cooled to room temperature, after centrifugation under 80 ~ 120 ° of C vacuumize 12 ~ 24h;
3) by step 2) in the product that obtains be placed in tube furnace, heat-treat with 2 ° of C/min temperature programming to 300 ~ 500 ° C under argon gas atmosphere, then be cooled to room temperature, the hollow porous nickel oxide composite material of Surface coating N doping carbon-coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310723668.4A CN103647072B (en) | 2013-12-25 | 2013-12-25 | A kind of nickel oxide surfaces carbon/nitrogen content is than the preparation method of adjustable nitrogen-doped carbon integument |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310723668.4A CN103647072B (en) | 2013-12-25 | 2013-12-25 | A kind of nickel oxide surfaces carbon/nitrogen content is than the preparation method of adjustable nitrogen-doped carbon integument |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103647072A CN103647072A (en) | 2014-03-19 |
| CN103647072B true CN103647072B (en) | 2015-12-30 |
Family
ID=50252263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310723668.4A Expired - Fee Related CN103647072B (en) | 2013-12-25 | 2013-12-25 | A kind of nickel oxide surfaces carbon/nitrogen content is than the preparation method of adjustable nitrogen-doped carbon integument |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103647072B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104282896A (en) * | 2014-09-18 | 2015-01-14 | 东莞市翔丰华电池材料有限公司 | Nitrogen-doped carbon-coated graphite negative electrode material and preparation method thereof |
| CN104617291A (en) * | 2015-01-24 | 2015-05-13 | 复旦大学 | Uniform carbon coated lithium ion battery anode/cathode material and preparation method thereof |
| CN109014245B (en) * | 2018-09-03 | 2020-04-07 | 大连理工大学 | Nitrogen-doped carbon-coated magnetic nanoparticle composite microsphere and preparation method thereof |
| JP2022553045A (en) * | 2019-10-21 | 2022-12-21 | 中国石油化工股▲ふん▼有限公司 | Carbon-coated nickel oxide nanocomposites, their production methods and applications |
| CN113117719B (en) * | 2021-04-12 | 2022-06-14 | 中山大学 | Nickel-based metal nano material with unconventional crystalline phase and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417823A (en) * | 2008-11-14 | 2009-04-29 | 中国科学院上海硅酸盐研究所 | Wet chemical preparation method of nickel oxide hollow microsphere without template |
| CN101962211A (en) * | 2010-10-26 | 2011-02-02 | 南京工业大学 | Method for preparing nano nickel bicarbonate |
| CN103274453A (en) * | 2013-05-14 | 2013-09-04 | 广东精进能源有限公司 | Method for preparing carbon-coated nitrogen-doped lithium titanate composite material by novel carbon-nitrogen-doped titanium dioxide and application for same |
-
2013
- 2013-12-25 CN CN201310723668.4A patent/CN103647072B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417823A (en) * | 2008-11-14 | 2009-04-29 | 中国科学院上海硅酸盐研究所 | Wet chemical preparation method of nickel oxide hollow microsphere without template |
| CN101962211A (en) * | 2010-10-26 | 2011-02-02 | 南京工业大学 | Method for preparing nano nickel bicarbonate |
| CN103274453A (en) * | 2013-05-14 | 2013-09-04 | 广东精进能源有限公司 | Method for preparing carbon-coated nitrogen-doped lithium titanate composite material by novel carbon-nitrogen-doped titanium dioxide and application for same |
Non-Patent Citations (2)
| Title |
|---|
| "Hierarchical NiO hollow microspheres assembled from nanosheet-stacked nanoparticles and their application in a gas sensor";Guoxing Zhu et al;《RSC Advances》;20120128;第2卷;第4236-4241页 * |
| "Porous Li4Ti5O12 coated with N-doped carbon from Ionic Liquids for Li-ion Batteries";Liang Zhao et al;《Advanced materials》;20110102;第23卷;第1385-1388页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103647072A (en) | 2014-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105742602B (en) | A kind of sodium-ion battery cathode Sn/MoS2/ C composite and preparation method thereof | |
| CN103682327B (en) | Based on the lithium ion battery and preparation method thereof of the hollow porous nickel oxide composite material of N doping carbon-coating parcel | |
| CN103427073B (en) | A kind of preparation method of the mesoporous Si/C complex microsphere as lithium cell cathode material | |
| CN103326007B (en) | The preparation method of three-dimensional graphite thiazolinyl tin dioxide composite material and application thereof | |
| CN103413925B (en) | Curling molybdenum trioxide nano band of Graphene and its preparation method and application | |
| CN103647072B (en) | A kind of nickel oxide surfaces carbon/nitrogen content is than the preparation method of adjustable nitrogen-doped carbon integument | |
| CN102437314B (en) | Foam metal/lithium iron phosphate integral electrode with three-dimensional structure, preparation method thereof and lithium ion battery using integral electrode as positive pole piece | |
| CN103259018B (en) | Preparation method of porous graphite flake applied to super-electric negative pole of lithium battery | |
| CN103441246B (en) | The preparation method of the graphene-based tin dioxide composite material of three-dimensional N doping and application thereof | |
| CN107093732A (en) | It is a kind of for lithium iron phosphate/carbon nano-tube nano composite of anode material of lithium battery and preparation method thereof | |
| CN104201363A (en) | Carbon-coated Li3VO4 lithium ion battery anode material and preparation method thereof | |
| CN104091937A (en) | Lithium titanate-coated surface-treated graphite negative electrode material, preparation method and application of negative electrode material | |
| CN103682277B (en) | Hollow porous nickel oxide composite material of N doping carbon-coating parcel and preparation method thereof | |
| CN105006551A (en) | Stannic phosphide/graphene composite cathode material for sodium-ion battery and preparation method thereof | |
| CN107507963A (en) | A kind of preparation method of graphene coated artificial plumbago negative pole material | |
| CN110416509A (en) | A kind of lithium ion battery negative material of height ratio capacity and preparation method thereof | |
| CN102185147A (en) | Nano iron phosphate hollow sphere/graphene composite material and preparation method thereof | |
| CN106410153A (en) | Titanium nitride-cladded nickel titanate composite material as well as preparation method and application thereof | |
| CN107068994A (en) | A kind of preparation method of the carbon load nitridation iron complexes anode material of lithium-ion battery of N doping | |
| CN102097616A (en) | Preparation method of high-energy and high-power density nano-scale lithium iron phosphate powder | |
| CN104617280A (en) | Adhesive-free graphene/silicon electrode for lithium ion battery and preparation method thereof | |
| CN106025241A (en) | Graphene aerogel loaded lithium iron phosphate porous composite material and preparation method thereof | |
| CN107681147A (en) | A kind of preparation method of solid electrolyte coating modification anode material for lithium-ion batteries and application | |
| CN105244503A (en) | Method for preparing graphene-grading-modification spherical sodium-ion battery electrode material | |
| CN106848220A (en) | A kind of preparation method of Graphene iron oxide graphene composite structure cell negative electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151230 Termination date: 20181225 |