CN103762349B - Nucleocapsid structure CuO/Cu nano wire negative material and its preparation method and application - Google Patents
Nucleocapsid structure CuO/Cu nano wire negative material and its preparation method and application Download PDFInfo
- Publication number
- CN103762349B CN103762349B CN201410037927.2A CN201410037927A CN103762349B CN 103762349 B CN103762349 B CN 103762349B CN 201410037927 A CN201410037927 A CN 201410037927A CN 103762349 B CN103762349 B CN 103762349B
- Authority
- CN
- China
- Prior art keywords
- cuo
- nano
- solution
- preparation
- wire
- 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.)
- Active
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
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides 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
- 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
The present invention discloses a kind of nucleocapsid structure CuO/Cu nano wire negative material and its preparation method and application, it is mainly composited by CuO and Cu, and Cu is nanowire-type, and it is flower-shaped that CuO is, and Cu is as the kernel of nano wire negative material, and CuO is coated on Cu outer surface to form nucleocapsid structure. Its preparation method comprises: first Schweinfurt green, ethylenediamine and hydrazine hydrate solution are joined in sodium hydroxide solution, sealing is placed on heating in 60 DEG C～80 DEG C water-baths and obtains copper nano-wire suspension, then isolate copper nano-wire, after washing, immerse in hydrogen peroxide, make copper nano-wire surface in situ grow flower-shaped CuO, after separating, washing, be dried, obtain nucleocapsid structure CuO/Cu nano wire negative material. Nucleocapsid structure CuO/Cu nano wire negative material of the present invention can be used for preparing the high negative electrode for lithium ion battery of leading, and has better electric conductivity and mechanical property.
Description
Technical field
The invention belongs to lithium ion battery negative material technical field, relate in particular to a kind of CuO/Cu nano wire negative material andPreparation method and application.
Background technology
Along with lithium ion battery uses and needs as big or middle power power-supply on electric automobile, hybrid vehicle and electric bicycleThe continuous increase of asking, has also proposed requirements at the higher level to the performance of its positive and negative pole material. At present, the negative pole material of commercial Li-ion batteriesMaterial is mainly material with carbon element, sends out but its limited theoretical capacity (372mAh/g) can not meet high performance lithium ion battery of new generationThe requirement of exhibition.
CuO has higher lithium storage content, if think 2 lithium ions of 1 CuO molecule embedding, its theoretical capacity is670mAh/g, is the more than 2 times of graphite cathode material, and its cheap and easy to get, nontoxic, easily storage. Thereby CuOHave development potentiality and application prospect as lithium ion battery negative material. But, because CuO electric conductivity is poor, and in deintercalationIn lithium process, there is very large Volume Changes, thereby cause the efflorescence of CuO particle, lose effectively and electrically contact, reduced active matterThe utilization rate of matter, therefore its irreversible capacity is large and cycle performance is poor first. Nanometer is to improve the circulation of CuO negative materialThe effective ways of stability, not only can reduce the cubical expansivity in storage lithium process, can also improve its large current density performance.Nanometer CuO and C Material cladding can effectively be improved to the cyclical stability of CuO negative material, for example, with 3D network structureGraphite is compound can reduce volumetric expansion, provides good conductive and mechanical properties with CNT, carbon fiber etc. are compound. SoAnd, comparing above-mentioned material, CuO and metal composite have more advantage, because metal has better electric conductivity and toughness, traceThe existence of metal has positive work improving the electronic conductivity of CuO and slow down CuO in charge and discharge process aspect Volume ChangesWith, can improve that CuO is intergranular to be electrically contacted, reduce the efflorescence of CuO in cyclic process, thereby greatly improve following of materialRing performance. The people such as the such as Feng Ran of Zhejiang University utilize oxidization of copper powder method in air to prepare CuO/Cu composite powder, as lithium fromAfter sub-cell negative electrode material application, good chemical property [Feng Ran, Gao Chunxia etc., nanometer CuO/Cu negative material are shownThermal oxide preparation and structure thereof and chemical property, " Materials Science and Engineering journal ", 2012,2:245-249]; In addition,CN101722314A Chinese patent literature has been reported a kind of template synthesis Cu2The technical scheme of O/Cu complex microsphere powder;CN103454328A Chinese patent literature has also been reported a kind of glucose detection CuO/Cu membrane electrode piece preparation method,Be oxidized in hydrothermal reaction kettle by copper base and generate CuO film. But, in practical application, often find: granular pattern CuO/CuComposite powder is as lithium ion battery negative material, very limited to the raising of electric conductivity, because copper particle is distributed in CuO granuleIn, can not form conductive network; And film type electrodes is unfavorable for processing and the assembling of electrode, and preparation process needs high temperature highBe installed with standbyly, technique is more complicated. CN102629685A Chinese patent literature has been reported a kind of taking copper acetate, pyrrole monomer as formerMaterial is prepared Cu under HTHP2The method of O/Cu/PPy nano wire lithium ion battery negative material, but this composite nano-lineDo not form nucleocapsid structure, and utilized high-temperature high-pressure apparatus, cost is higher, is difficult for extension and produces.
Therefore, develop that a kind of preparation method is simple, electric conductivity and mechanical property is better, practicality is stronger Metal Substrate CuO negative poleMaterial is that those skilled in the art pursue always.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the nucleocapsid structure that a kind of specific area is large, electric conductivity is stronger is providedCuO/Cu nano wire negative material, also correspondingly provides that a kind of method is simple, controlled, technical process non-pollutant discharge, costThe preparation method of low nucleocapsid structure CuO/Cu nano wire negative material, also provides a kind of nucleocapsid structure CuO/Cu nano wire negativeUtmost point material, in the high application of leading in negative electrode for lithium ion battery of preparation, has better its powdery type negative material of comparing otherElectric conductivity and mechanical property, can show better combination property and practicality.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of nucleocapsid structure CuO/Cu nano wire negative pole materialMaterial, described nano wire negative material is mainly composited by CuO and Cu, and described metal Cu is nanowire-type, described CuOBe flower-shaped, and the metal Cu of nanowire-type is as the kernel of nano wire negative material, flower-shaped CuO is coated on nanowire-typeMetal Cu outer surface is to form nucleocapsid structure.
In above-mentioned nucleocapsid structure CuO/Cu nano wire negative material, preferred, the diameter of the metal Cu of described nanowire-type is50nm～150nm, length is 5 μ m～100 μ m, CuO is 100nm～320nm at the coated thickness of metal Cu outer surface.
In above-mentioned nucleocapsid structure CuO/Cu nano wire negative material, preferred, described flower-shaped CuO is the side with growth in situFormula is coated on metal Cu outer surface.
As a total technical conceive, the present invention also provides a kind of system of above-mentioned nucleocapsid structure CuO/Cu nano wire negative materialPreparation Method, comprises the following steps:
(1) Schweinfurt green solution, ethylenediamine solution and hydrazine hydrate solution are joined in sodium hydroxide solution, sealing be placed on 60 DEG C～In 80 DEG C of water-baths, after heated at constant temperature, obtain copper nano-wire suspension;
(2) in the copper nano-wire suspension obtaining in step (1), isolate the copper nano-wire of suspension, and wash by deionized waterWash, then immerse in hydrogen peroxide and react, make copper nano-wire surface in situ grow flower-shaped CuO, obtain CuO/Cu nanometerLine;
(3) isolate the CuO/Cu nano wire obtaining in step (2), with being dried after deionized water washing, obtain nucleocapsidStructure C uO/Cu nano wire negative material.
Above-mentioned preparation method, preferred, in described step (1), described Schweinfurt green solution, ethylenediamine solution and hydrazine hydrate are moltenLiquid is at room temperature to join according to the order of sequence successively in sodium hydroxide solution.
Above-mentioned preparation method, preferred, in described step (1), the molar concentration of described Schweinfurt green solution is 0.1M～0.5M,Described ethylenediamine solution is the anhydrous ethylenediamine solution of mass fraction more than 99%, and the mass fraction of described hydrazine hydrate solution is without spyNot requirement, generally gets final product (for example 80wt%) by the mass concentration of commercial preparation, and the molar concentration of described sodium hydroxide solution is 10 M～15M。
Above-mentioned preparation method, preferred, in described step (1), described Schweinfurt green solution, ethylenediamine solution, hydrazine hydrate are moltenThe volumetric usage ratio of liquid, sodium hydroxide solution is controlled at 10～50:2.5～5:0.5～1:1000; The time of heated at constant temperature is controlled at0.5h～2h。
Above-mentioned preparation method, preferred, in described step (2), the mass concentration of described hydrogen peroxide is 40%～80%, anti-Answer temperature to be controlled at 10 DEG C～50 DEG C, the reaction time is controlled at 0.2h～2h.
Above-mentioned preparation method, preferred, in described step (3), baking temperature is controlled at 160 DEG C～200 DEG C, when dryBetween be controlled at 5h～10h.
As a total technical conceive, the present invention also provides a kind of nucleocapsid structure CuO/Cu nano wire negative pole of the invention described aboveThe application of material in the high conductive lithium ion negative electrode battery of preparation.
Technical scheme of the present invention is based on following principle and thinking: generally believe that CuO has as negative material well excellentGesture, but its poorly conductive, be creatively combined with each other the metal of good conductivity in the present invention with it, utilize the conduction of metalProperty improves the electric conductivity of CuO, and based on this thinking, it is compound that we select CuO and metal Cu to carry out especially, forms at materialOn first make improvement; Meanwhile, with respect to traditional granular pattern electrode material, lay special stress on of the present invention the nucleocapsid of nanowire-typeStructure C uO/Cu, one is nano wire copper, the 2nd, nucleocapsid cladded type structure, this design feature is led preparation Stability Analysis of Structures, heightElectricity electrode material is highly profitable.
Compared with prior art, the invention has the advantages that:
(1) the present invention creatively loads on cupric oxide original position on nanowire-type metallic copper, and this not only makes preparation method simpleControlled, preparation temperature is low, and technical process non-pollutant discharge, and cost is low, suitability for scale production; The present invention selectsRaw material is also beneficial to moulding and obtains the nano wire negative material of nucleocapsid structure of the present invention especially;
(2) the CuO/Cu nano wire negative material that prepared by the inventive method has nucleocapsid structure, and flower-like nanometer CuO is coatedIn Cu nanowire surface, this compares single-phase CuO, and not only specific area increases, and the electric conductivity of composite nano-line also greatlyStrengthen; Compare granular pattern composite powder, the special construction of product of the present invention and linear presence more easily form conductive network, provideElectronics transmission channels faster, nucleocapsid structure not only can provide high active surface, and well fixation of C uO of energy, thereforeThere is better electric conductivity and mechanical property;
(3) the CuO/Cu nano wire negative material that prepared by the inventive method has special structure and pattern because of it, compares otherPowdery type negative material there is better electric conductivity and mechanical property, it is as showing after lithium ion battery negative materialBetter combination property and practicality.
Brief description of the drawings
Fig. 1 is the SEM photo of Cu nano wire in the embodiment of the present invention 1.
Fig. 2 is the SEM photo of CuO/Cu nano wire in the embodiment of the present invention 1.
Fig. 3 is the TEM photo of CuO/Cu nano wire in the embodiment of the present invention 1.
Fig. 4 is the XRD result of CuO/Cu nano wire in the embodiment of the present invention 1.
Fig. 5 is the SEM photo of CuO/Cu nano wire in the embodiment of the present invention 2.
Fig. 6 is the TEM photo of CuO/Cu nano wire in the embodiment of the present invention 2.
Detailed description of the invention
For the ease of understanding the present invention, below in connection with Figure of description and preferred embodiment to the present invention do more comprehensively, carefulGround is described, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, all technical terms of hereinafter using are identical with the implication that those skilled in the art understand conventionally.Technical term used herein, just in order to describe the object of specific embodiment, is not to be intended to limit protection model of the present inventionEnclose.
Unless otherwise specified, hereinafter any raw material used, reagent etc. all can buy from market maybe can be by knownMethod prepares.
Embodiment 1:
A kind of nucleocapsid structure CuO/Cu nano wire negative material of the present invention, this nano wire negative material is mainly by CuO and CuBe composited, wherein, metal Cu is nanowire-type, and it is flower-shaped that CuO is, and the metal Cu of nanowire-type is as nano wire negative poleThe kernel of material, flower-shaped CuO is coated on the metal Cu outer surface of nanowire-type to form nucleocapsid structure. Metal Cu's is straightFootpath is 140nm left and right, and length is 30 μ m～50 μ m, and CuO is about 300nm at the coated thickness of metal Cu outer surface. FlowerThe CuO of shape is coated on metal Cu outer surface in the mode of growth in situ.
The nucleocapsid structure CuO/Cu nano wire cathode material preparation method of above-mentioned the present embodiment, specifically comprises the following steps:
(1) purchase Schweinfurt green solution, the sodium hydroxide solution of 15M, the anhydrous second two of mass fraction more than 99% of 0.1MThe hydrazine hydrate solution of amine aqueous solution and 80wt%, successively by 50mL Schweinfurt green solution, 5mL anhydrous ethylenediamine solution, 0.5mLHydrazine hydrate solution joins in the container that fills 1000mL sodium hydroxide solution, puts into 80 DEG C of water-baths after sealing, and constant temperature addsHot 2h, obtains copper nano-wire suspension;
(2) in the copper nano-wire suspension obtaining in step (1), isolate the copper nano-wire (referring to Fig. 1) of suspension, useAfter deionized water rinsing, directly immerse 80% H2O2In solution, copper nano-wire surface starts to occur oxidation reaction, reaction temperatureBeing controlled at 20 DEG C of reaction time is controlled at 2h, makes copper nano-wire surface in situ grow flower-shaped CuO, obtains CuO/Cu compoundNano wire;
(3) isolate the CuO/Cu composite nano-line obtaining in step (2), with putting into 200 DEG C of baking ovens after deionized water washingIn dry 10h, obtain nucleocapsid structure CuO/Cu nano wire negative material.
The nucleocapsid structure CuO/Cu nano wire negative material that the present embodiment is made detects, and testing result is as Fig. 2, Fig. 3Shown in Fig. 4, from Fig. 2 and Fig. 3, the diameter 140nm of copper nano-wire, length is 30 μ m～50 μ m, after oxidation,The obvious flower-like nanometer cupric oxide of copper nano-wire area load forms nucleocapsid structure, the about 300nm of its load thickness, XRD in Fig. 4Result show that the nucleocapsid structure CuO/Cu nano wire negative material of the present embodiment only contains CuO and Cu two-phase. Electrochemistry inspectionThe demonstration of survey result, product of the present invention has better electric conductivity and mechanical property.
Embodiment 2:
A kind of nucleocapsid structure CuO/Cu nano wire negative material of the present invention, this nano wire negative material is mainly by CuO and CuBe composited, wherein, metal Cu is nanowire-type, and it is flower-shaped that CuO is, and the metal Cu of nanowire-type is as nano wire negative poleThe kernel of material, flower-shaped CuO is coated on the metal Cu outer surface of nanowire-type to form nucleocapsid structure. Metal Cu's is straightFootpath is 60nm, and length is 5 μ m～15 μ m, and CuO is 100nm at the coated thickness of metal Cu outer surface. Flower-shaped CuOTo be coated on metal Cu outer surface in the mode of growth in situ.
The nucleocapsid structure CuO/Cu nano wire cathode material preparation method of above-mentioned the present embodiment, specifically comprises the following steps:
(1) purchase Schweinfurt green solution, the sodium hydroxide solution of 10M, the anhydrous second two of mass fraction more than 99% of 0.5MThe hydrazine hydrate solution of amine aqueous solution and 80wt%, successively by the water of 10mL Schweinfurt green solution, 3mL anhydrous ethylenediamine solution, 1mLClose hydrazine solution and join in the container that fills 1000mL sodium hydroxide solution, after sealing, put into 60 DEG C of water-baths, heated at constant temperature1.5h, obtains copper nano-wire suspension;
(2) in the copper nano-wire suspension obtaining in step (1), isolate the copper nano-wire of suspension, use deionized water rinsingAfter, directly immerse 40% H2O2In solution, copper nano-wire surface starts to occur oxidation reaction, and reaction temperature is controlled at 10 DEG C,The immersion reaction time is controlled at 0.2h, makes copper nano-wire surface in situ grow flower-shaped CuO, obtains CuO/Cu composite NanoLine;
(3) isolate the CuO/Cu composite nano-line obtaining in step (2), with putting into 160 DEG C of baking ovens after deionized water washingIn dry 8h, obtain nucleocapsid structure CuO/Cu nano wire negative material.
The nucleocapsid structure CuO/Cu nano wire negative material that the present embodiment is made detects, and testing result is as Fig. 5 and Fig. 6Shown in, from Fig. 5 and Fig. 6, the diameter 60nm of copper nano-wire, length is 5 μ m～15 μ m, after oxidation, copper nanometerThe obvious flower-like nanometer cupric oxide of line area load forms nucleocapsid structure, the about 100nm of its load thickness. Electrochemical Detection result is aobviousShow, product of the present invention has better electric conductivity and mechanical property.
Embodiment 3:
A kind of nucleocapsid structure CuO/Cu nano wire negative material of the present invention, this nano wire negative material is mainly by CuO and CuBe composited, wherein, metal Cu is nanowire-type, and it is flower-shaped that CuO is, and the metal Cu of nanowire-type is as nano wire negative poleThe kernel of material, flower-shaped CuO is coated on the metal Cu outer surface of nanowire-type to form nucleocapsid structure. Metal Cu's is straightFootpath is 75nm, and length is 70 μ m～100 μ m, and CuO is about 210nm at the coated thickness of metal Cu outer surface. Flower-shapedCuO is coated on metal Cu outer surface in the mode of growth in situ.
The nucleocapsid structure CuO/Cu nano wire cathode material preparation method of above-mentioned the present embodiment, specifically comprises the following steps:
(1) purchase Schweinfurt green solution, the sodium hydroxide solution of 12M, the anhydrous second of mass fraction more than 99% of 0.25MThe hydrazine hydrate solution of two amine aqueous solutions and 80wt%, successively by 20mL Schweinfurt green solution, 4mL anhydrous ethylenediamine solution, 0.7mLHydrazine hydrate solution join in the container that fills 1000mL sodium hydroxide solution, after sealing, put into 70 DEG C of water-baths, constant temperatureHeating 2h, obtains copper nano-wire suspension;
(2) in the copper nano-wire suspension obtaining in step (1), isolate the copper nano-wire of suspension, use deionized water rinsingAfter, directly immerse 60% H2O2In solution, copper nano-wire surface starts to occur oxidation reaction, and reaction temperature is controlled at 50 DEG C,The immersion reaction time is controlled at 1h, makes copper nano-wire surface in situ grow flower-shaped CuO, obtains CuO/Cu composite nano-line;
(3) isolate the CuO/Cu composite nano-line obtaining in step (2), with putting into 180 DEG C of baking ovens after deionized water washingIn dry 5h, obtain nucleocapsid structure CuO/Cu nano wire negative material.
The nucleocapsid structure CuO/Cu nano wire negative material that the present embodiment is made detects, and testing result shows, copper nanometerThe diameter 75nm of line, length is 70 μ m～100 μ m, after oxidation, the obvious flower-like nanometer oxidation of copper nano-wire area loadCopper forms nucleocapsid structure, the about 210nm of its load thickness.
Embodiment 4:
A kind of nucleocapsid structure CuO/Cu nano wire negative material of the present invention, this nano wire negative material is mainly by CuO and CuBe composited, wherein, metal Cu is nanowire-type, and it is flower-shaped that CuO is, and the metal Cu of nanowire-type is as nano wire negative poleThe kernel of material, flower-shaped CuO is coated on the metal Cu outer surface of nanowire-type to form nucleocapsid structure. Metal Cu's is straightFootpath is about 100nm, and length is 30 μ m～50 μ m, and CuO is about 300nm at the coated thickness of metal Cu outer surface. Flower-shapedCuO be coated on metal Cu outer surface in the mode of growth in situ.
The nucleocapsid structure CuO/Cu nano wire cathode material preparation method of above-mentioned the present embodiment, specifically comprises the following steps:
(1) purchase Schweinfurt green solution, the sodium hydroxide solution of 15M, the anhydrous second two of mass fraction more than 99% of 0.1MThe hydrazine hydrate solution of amine aqueous solution and 80wt%, successively by 2.5mL Schweinfurt green solution, 0.25mL anhydrous ethylenediamine solution, 0.03mLHydrazine hydrate solution join in the container that fills 50mL sodium hydroxide solution, after sealing, put into 80 DEG C of water-baths, constant temperature addsHot 2h, obtains copper nano-wire suspension;
(2) in the copper nano-wire suspension obtaining in step (1), isolate the copper nano-wire of suspension, use deionized water rinsingAfter, directly immerse 80% H2O2In solution, copper nano-wire surface starts to occur oxidation reaction, and reaction temperature is controlled at 30 DEG C,The immersion reaction time is controlled at 2h, makes copper nano-wire surface in situ grow flower-shaped CuO, obtains CuO/Cu composite nano-line;
(3) isolate the CuO/Cu composite nano-line obtaining in step (2), with putting into 200 DEG C of baking ovens after deionized water washingIn dry 10h, obtain nucleocapsid structure CuO/Cu nano wire negative material.
The nucleocapsid structure CuO/Cu nano wire negative material that the present embodiment is made detects, and testing result shows, copper nanometerThe diameter 100nm of line, length is 30 μ m～50 μ m, after oxidation, the obvious flower-like nanometer oxidation of copper nano-wire area loadCopper forms nucleocapsid structure, the about 300nm of its load thickness.
Claims (7)
1. the preparation method of a nucleocapsid structure CuO/Cu nano wire negative material, described nano wire negative material is mainly composited by CuO and Cu, described metal Cu is nanowire-type, described CuO is flower-shaped, and the metal Cu of nanowire-type is as the kernel of nano wire negative material, flower-shaped CuO is coated on the metal Cu outer surface of nanowire-type to form nucleocapsid structure, and described preparation method comprises the following steps:
(1) Schweinfurt green solution, ethylenediamine solution and hydrazine hydrate solution are joined in sodium hydroxide solution, sealing is placed in 60 DEG C～80 DEG C water-baths, obtains copper nano-wire suspension after heated at constant temperature;
(2) in the copper nano-wire suspension obtaining in step (1), isolate the copper nano-wire of suspension, and with deionized water washing, then immerse in hydrogen peroxide and react, make copper nano-wire surface in situ grow flower-shaped CuO, obtain CuO/Cu nano wire;
(3) isolate the CuO/Cu nano wire obtaining in step (2), with being dried after deionized water washing, obtain nucleocapsid structure CuO/Cu nano wire negative material.
2. preparation method according to claim 1, is characterized in that: the diameter of the metal Cu of described nanowire-type is 50nm～150nm, and length is 5 μ m～100 μ m, and CuO is 100nm～320nm at the coated thickness of metal Cu outer surface.
3. preparation method according to claim 1, is characterized in that: in described step (1), described Schweinfurt green solution, ethylenediamine solution and hydrazine hydrate solution are at room temperature to join according to the order of sequence successively in sodium hydroxide solution.
4. preparation method according to claim 3, it is characterized in that: in described step (1), the molar concentration of described Schweinfurt green solution is 0.1M～0.5M, described ethylenediamine solution is the anhydrous ethylenediamine solution of mass fraction more than 99%, and the molar concentration of described sodium hydroxide solution is 10M～15M.
5. preparation method according to claim 4, is characterized in that: in described step (1), the volumetric usage ratio of described Schweinfurt green solution, ethylenediamine solution, hydrazine hydrate solution, sodium hydroxide solution is controlled at 10～50:2.5～5:0.5～1:1000; The time of heated at constant temperature is controlled at 0.5h～2h.
6. according to the preparation method described in any one in claim 1～5, it is characterized in that: in described step (2), the mass concentration of described hydrogen peroxide is 40%～80%, and reaction temperature is controlled at 10 DEG C～50 DEG C, and the reaction time is controlled at 0.2h～2h.
7. according to the preparation method described in any one in claim 1～5, it is characterized in that: in described step (3), baking temperature is controlled at 160 DEG C～200 DEG C, is controlled at 5h～10h drying time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410037927.2A CN103762349B (en) | 2014-01-26 | 2014-01-26 | Nucleocapsid structure CuO/Cu nano wire negative material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410037927.2A CN103762349B (en) | 2014-01-26 | 2014-01-26 | Nucleocapsid structure CuO/Cu nano wire negative material and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103762349A CN103762349A (en) | 2014-04-30 |
| CN103762349B true CN103762349B (en) | 2016-05-11 |
Family
ID=50529550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410037927.2A Active CN103762349B (en) | 2014-01-26 | 2014-01-26 | Nucleocapsid structure CuO/Cu nano wire negative material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103762349B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104466131B (en) * | 2014-11-28 | 2017-01-18 | 长沙矿冶研究院有限责任公司 | MnO2-metal nanowire composite cathode material adopting core-shell structure as well as preparation method and application thereof |
| CN104959626B (en) * | 2015-06-30 | 2017-02-22 | 厦门大学 | Method for preparing multifunctional core-shell nano-material by using alloy to wrap copper nanowires |
| KR102263467B1 (en) * | 2017-07-19 | 2021-06-11 | 주식회사 엘지에너지솔루션 | Electrode without Electrode Current Collector and Secondary Battery Having the Same |
| CN107611389B (en) * | 2017-08-31 | 2020-04-24 | 上海空间电源研究所 | Copper oxide-based composite positive electrode material for thermal battery and preparation method and application thereof |
| CN109638224B (en) * | 2018-11-29 | 2021-12-31 | 西交利物浦大学 | Preparation method and application of copper-carbon-silicon composite negative plate |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502770B (en) * | 2011-10-21 | 2014-09-24 | 中国科学院过程工程研究所 | Flower-like copper oxide catalyst and preparation method and application thereof |
| CN102709056A (en) * | 2012-05-02 | 2012-10-03 | 中国矿业大学(北京) | Current collector of energy storage device, and preparation method of current collector |
-
2014
- 2014-01-26 CN CN201410037927.2A patent/CN103762349B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103762349A (en) | 2014-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103326007B (en) | The preparation method of three-dimensional graphite thiazolinyl tin dioxide composite material and application thereof | |
| CN104835654B (en) | A kind of three-dimensional nitrogen-doped graphene/molybendum disulfide complexes and preparation method thereof | |
| CN106099069B (en) | A kind of sodium-ion battery cathode SnS/C composite material and preparation method | |
| CN103762349B (en) | Nucleocapsid structure CuO/Cu nano wire negative material and its preparation method and application | |
| Xu et al. | Understanding the effect of polypyrrole and poly (3, 4-ethylenedioxythiophene) on enhancing the supercapacitor performance of NiCo 2 O 4 electrodes | |
| CN103441246B (en) | The preparation method of the graphene-based tin dioxide composite material of three-dimensional N doping and application thereof | |
| CN105826527A (en) | Porous silicon-carbon composite material and preparation method and application thereof | |
| CN105244191A (en) | Manganese cobalt oxide porous nanometer sheet/foam nickel compound electrode material preparation method | |
| CN103346301A (en) | Preparation method and application of three-dimensional-structure graphene-base metal oxide composite material | |
| CN105720236A (en) | Foamed nickel self-supported flake-shaped Ni3P/C composite material for sodium ion battery negative electrode and preparation method for composite material | |
| CN105390674A (en) | Iron diselenide/sulfur-doped graphene anode composite material for sodium-ion battery and preparation method of iron diselenide/sulfur-doped graphene anode composite material | |
| CN106971855B (en) | A kind of nickel ferrite based magnetic loaded nanoparticle electrode material and preparation method and purposes | |
| CN105958037B (en) | Sodium-ion battery cathode copper sulfide/graphene composite material and preparation method | |
| CN105244192A (en) | Magnesium cobaltite porous nanowire array/ nickel foam composite electrode material preparation method | |
| CN107068994A (en) | A kind of preparation method of the carbon load nitridation iron complexes anode material of lithium-ion battery of N doping | |
| Zhang et al. | Preparation of a porous graphite felt electrode for advance vanadium redox flow batteries | |
| CN106848220B (en) | A kind of preparation method of graphene-iron oxide-graphene composite structure cell negative electrode material | |
| CN109786135A (en) | A kind of copper oxide@nickel molybdate/foam copper combination electrode material and preparation method thereof | |
| CN104701496A (en) | SnO2/CMK-3 nanometer composite lithium-ion battery negative electrode material preparation method | |
| CN104821397A (en) | Sea urchin-like lithium titanate microsphere preparation method | |
| CN108682564B (en) | A kind of Ni-C composite material and preparation method for supercapacitor | |
| CN104466178A (en) | Hierarchical mesoporous sodium vanadate bent nanowire as well as preparation method and application thereof | |
| CN109119257A (en) | The preparation method of self-supporting nano-sheet iron cobalt boron electrode material for super capacitor | |
| CN108806995A (en) | A kind of g-C3N4@NiCo2O4The preparation method of nucleocapsid | |
| CN105118683A (en) | Preparation method of cobalt molybdate composite manganese dioxide electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | 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 |