CN106876658A - A kind of preparation method of Hollow Nickel rod/carbon ball array electrode - Google Patents

A kind of preparation method of Hollow Nickel rod/carbon ball array electrode Download PDF

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CN106876658A
CN106876658A CN201710193108.0A CN201710193108A CN106876658A CN 106876658 A CN106876658 A CN 106876658A CN 201710193108 A CN201710193108 A CN 201710193108A CN 106876658 A CN106876658 A CN 106876658A
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nickel sheet
nickel
micron bar
zno
shell structure
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陈明华
亓美丽
陈庆国
殷景华
周兆兴
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Harbin University of Science and Technology
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Harbin University of Science and Technology
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    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/049—Manufacturing of an active layer by chemical means
    • H01M4/0497—Chemical precipitation
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

A kind of preparation method of Hollow Nickel rod/carbon ball array electrode, it is related to a kind of preparation method of electrode.All it is, as granular powder application, and to be difficult to be assembled into self-supporting array the invention aims to solve CNSs, it is impossible to realize the problem of core shell structure flexible electrode.Method：First, the nickel sheet of area load ZnO micron bar arrays is prepared；2nd, the nickel sheet of the ZnO/Ni micron bar arrays of area load core shell structure is prepared；3rd, the nickel sheet of the Ni/C micron bar arrays of area load core shell structure, the as nickel sheet of the Ni/C micron bar arrays of the area load core shell structure for obtaining, Hollow Nickel rod/carbon ball array electrode are prepared.In 50mA g‑1Current density under, the capacity of Hollow Nickel rod/carbon ball array electrode prepared by the present invention is up to 170mAh g‑1.The present invention is suitable for preparing Hollow Nickel rod/carbon ball array electrode.

Description

A kind of preparation method of Hollow Nickel rod/carbon ball array electrode
Technical field
The present invention relates to a kind of preparation method of electrode.
Background technology
The advantages of lithium ion battery is due to its energy density higher, memory-less effect and be widely used in various necks Domain.People extend cycle life improving the energy density of lithium ion battery, stable operating voltage, etc. aspect done and much exerted Power.
Carbon material because of its low cost, rich content, excellent chemical property and it is environment-friendly the features such as turn into most by joyous One of lithium ion battery active material met.CNT, Graphene, fullerene and Nano carbon balls (CNSs) belong to carbon family. For many years, researcher enters to carbon materials such as Graphene and CNSs in fields such as lithium ion battery, ultracapacitor, catalyst Row numerous studies, and have made some progress.CNSs not only can directly be used as the electrode material of battery or ultracapacitor, and And be widely used as with metal (for example：Platinum, rubidium, copper etc.), nonmetallic, metal oxide (for example：TiO2/CNSs、 SnO2/CNSs、MnO/CNSs、Co3O4/ CNSs and Fe2O3/ CNSs) compound rest and template.The many composites prepared It is used to improve the functional characteristic of material.Meanwhile, the side of method or non-template of the above-mentioned material either with CNSs as template Method, is all exist with powder, it is difficult to which CNSs is assembled into self-supporting array flexible electrode.
The content of the invention
All it is, as granular powder application, and to be difficult to be assembled into self-supporting battle array the invention aims to solve CNSs Row, it is impossible to realize the problem of core shell structure flexible electrode, and a kind of preparation method of Hollow Nickel rod/carbon ball array electrode is provided.
A kind of preparation method of Hollow Nickel rod/carbon ball array electrode, is specifically realized by the following steps：
First, the nickel sheet of area load ZnO micron bar arrays is prepared：
1. nickel sheet is cleaned by ultrasonic 3 times~5 times first by acetone, absolute ethyl alcohol is reused and nickel sheet is cleaned by ultrasonic 3 times ~5 times, then be baked to, obtain the nickel sheet of cleaning；
Step one 1. described in nickel sheet thickness be 0.15mm~0.5mm；
2., by ZnNO3·6H2O is added in deionized water, then carries out ultrasonic disperse 15min~20min, adds quality Fraction is 25%~28% ammoniacal liquor, obtains mixed solution A；
Step one 2. described in ZnNO3·6H2The amount of the material of O is 0.005mol with the volume ratio of deionized water: (50mL~60mL)；
Step one 2. described in ZnNO3·6H2The amount and mass fraction of the material of O are the body of 25%~28% ammoniacal liquor Product is than being 0.005mol:(10mL~20mL)；
On one surface of the clean nickel sheet obtained during 1. Kapton Tape 3., is pasted into step one, then immerse To step one 2. in react 6h~8h in the mixed solution A that obtains, then at being 90 DEG C in temperature, using distilled water to nickel after taking-up Piece is rinsed 3 times~5 times, obtains the nickel sheet of area load ZnO micron bar arrays；
2nd, the nickel sheet of the ZnO/Ni micron bar arrays of area load core shell structure is prepared：
1., by NiSO4And NH4Cl is added in deionized water, then carries out ultrasonic disperse 15min~20min, is mixed Solution B；
Step 2 1. described in NiSO4The volume ratio of amount and deionized water of material be 0.005mol:(80mL~ 120mL)；
Step 2 1. described in NH4The amount of the material of Cl is 0.001mol with the volume ratio of deionized water:(80mL~ 120mL)；
, used as working electrode, nickel sheet is used as right for the nickel sheet of the area load ZnO micron bar arrays that 2., will be obtained in step one Electrode, electro-deposition is carried out in the mixed solution B obtained in being immersed in step 2 1. by working electrode and to electrode, then will load The nickel sheet of ZnO micron bar arrays is taken out, and reuses distilled water flushing 3 times~5 times, obtains the ZnO/Ni of area load core shell structure The nickel sheet of micron bar array；
Step 2 2. described in electro-deposition be on electrochemical workstation complete, wherein current density be 2.0~ 3.0mA cm-2, electrodeposition time is 250s~350s；
3rd, the nickel sheet of the Ni/C micron bar arrays of area load core shell structure is prepared；
1., glucose is added in deionized water, then carries out ultrasonic disperse 15min~20min, obtain mixed solution C；
Step 3 1. described in the volume ratio of amount and deionized water of material of glucose be 0.2mol:(80mL~ 120mL)；
It is sub- that the nickel sheet of the ZnO/Ni micron bar arrays of the area load core shell structure that 2., will be obtained in step 2 posts polyamides The face of amine adhesive tape is fixed on slide, then is immersed in dress by the downward form of the ZnO/Ni micron bar arrays of load core shell structure In having a polytetrafluoroethylliner liner of mixed solution C, then polytetrafluoroethylliner liner is put into autoclave；
3. autoclave, is reacted into 2h~5h in the case where temperature is for 150 DEG C~200 DEG C, room temperature is cooled to, is reacted Thing；Reactant is taken out, distilled water flushing is reused 3 times~5 times, then by reactant argon gas atmosphere and temperature be 450 DEG C~ 40min~90min is heat-treated at 550 DEG C, the nickel sheet of the Ni/C micron bar arrays of area load core shell structure is obtained, it is as hollow Nickel rod/carbon ball array electrode.
Principle of the invention and advantage：
First, the length that the present invention synthesizes ZnO micron bars array and make it vertical by the method for chemical bath deposition CBD first exists In nickel sheet.Then prepare core shell structure on ZnO micron bar arrays by the method for electrochemical deposition ED ZnO/Ni microns Rod array, then by hydro-thermal method and the method for annealing, prepare the Ni/C micron bar arrays of core shell structure.This hollow nickel is micro- Mitron array is directly connected with collector, it is not necessary to any conductive additive, improves the energy density of battery.It is prior Be, in subsequent cycle performance test, with current density as 50mA/g under conditions of, the Hollow Nickel rod/carbon of present invention preparation Capacity retention can be very good after the circle of discharge and recharge 100 for ball array electrode；
2nd, in 50mA g-1Current density under, the present invention prepare Hollow Nickel rod/carbon ball array electrode charging capacity Up to 170mAh g-1；
3rd, Hollow Nickel rod/carbon ball array electrode prepared by the present invention remains greater than 148mAh after 100 cycle periods g-1Capacity, this shows good cycle performance, is remained above 86.8% capacity.
The present invention is suitable for preparing Hollow Nickel rod/carbon ball array electrode.
Brief description of the drawings
Fig. 1 is to prepare the schematic diagram of Hollow Nickel rod/carbon ball array electrode in embodiment one, and 1 is the step of embodiment one in Fig. 1 The nickel sheet of the area load ZnO micron bar arrays obtained in, 2 is the area load nucleocapsid knot obtained in the step 2 of embodiment one The nickel sheet of the ZnO/Ni micron bar arrays of structure, 3 is micro- for the Ni/C of the area load core shell structure obtained in the step 3 of embodiment one The nickel sheet of rice rod array；
Fig. 2 is ZnO micron bar arrays in the nickel sheet of the area load ZnO micron bar arrays obtained in the step one of embodiment one Amplify 5000 times of SEM figures；
Fig. 3 is ZnO micron bar arrays in the nickel sheet of the area load ZnO micron bar arrays obtained in the step one of embodiment one Amplify 10000 times of SEM figures；
Fig. 4 is in the nickel sheet of the ZnO/Ni micron bar arrays of area load core shell structure obtained in the step 2 of embodiment one The ZnO/Ni micron bars array of core shell structure amplifies 5000 times of SEM figures；
Fig. 5 is in the nickel sheet of the ZnO/Ni micron bar arrays of area load core shell structure obtained in the step 2 of embodiment one The ZnO/Ni micron bars array of core shell structure amplifies 10000 times of SEM figures；
Fig. 6 is the nickel sheet coker of the Ni/C micron bar arrays of area load core shell structure obtained in the step 3 of embodiment one The Ni/C micron bars array of shell structure amplifies 3000 times of SEM figures；
Fig. 7 is the nickel sheet coker of the Ni/C micron bar arrays of area load core shell structure obtained in the step 3 of embodiment one The Ni/C micron bars array of shell structure amplifies 8000 times of SEM figures；
Fig. 8 is single in the nickel sheet of the Ni/C micron bar arrays of area load core shell structure obtained in the step 3 of embodiment one The Ni/C micron bars array of individual rupture amplifies 8000 times of SEM figures；
Fig. 9 is the nickel sheet coker of the Ni/C micron bar arrays of area load core shell structure obtained in the step 3 of embodiment one The Ni/C micron bars array of shell structure amplifies 8000 times of TEM figures；
Figure 10 is in the nickel sheet of the Ni/C micron bar arrays of area load core shell structure obtained in the step 3 of embodiment one The Ni/C micron bar arrays of core shell structure amplify 100,000 times of TEM figures；
Figure 11 is in the nickel sheet of the Ni/C micron bar arrays of area load core shell structure obtained in the step 3 of embodiment one The Ni/C micron bar arrays of core shell structure amplify 1,000,000 times of HRTEM figures；
Figure 12 is Raman spectrogram, and 1 is the Raman curve of the ZnO/Ni micron bar arrays of core shell structure in Figure 12, and 2 is core The Raman curve of the Ni/C micron bar arrays of shell structure, A is the absworption peak of ZnO, and D is the SP3 keys of Nano carbon balls, and G is carbon nanometer The SP2 keys of ball；
Figure 13 is XRD curves, and 1 is the XRD curves of the ZnO/Ni micron bar arrays of core shell structure in Figure 13, and 2 is nucleocapsid knot The XRD curves of the Ni/C micron bar arrays of structure, " ◆ " is the diffraction maximum of ZnO；
Figure 14 is the cyclic curve of Hollow Nickel rod/carbon ball array electrode that the step 3 of embodiment one is obtained, and " " is charging, "○" is electric discharge；
Figure 15 is the curve of double curvature of Hollow Nickel rod/carbon ball array electrode that the step 3 of embodiment one is obtained, and A is electricity in Figure 15 Current density is 50mAg-1Under curve of double curvature, B be current density be 100mAg-1Under curve of double curvature, C is for current density 200mAg-1Under curve of double curvature, D be current density be 500mAg-1Under curve of double curvature, E be current density be 1000mAg-1Under Curve of double curvature, F be current density be 2000mAg-1Under curve of double curvature, G be current density be 50mAg-1Under multiplying power it is bent Line.
Specific embodiment
Specific embodiment one：Present embodiment is a kind of preparation method of Hollow Nickel rod/carbon ball array electrode, specifically Complete according to the following steps：
First, the nickel sheet of area load ZnO micron bar arrays is prepared：
1. nickel sheet is cleaned by ultrasonic 3 times~5 times first by acetone, absolute ethyl alcohol is reused and nickel sheet is cleaned by ultrasonic 3 times ~5 times, then be baked to, obtain the nickel sheet of cleaning；
Step one 1. described in nickel sheet thickness be 0.15mm~0.5mm；
2., by ZnNO3·6H2O is added in deionized water, then carries out ultrasonic disperse 15min~20min, adds quality Fraction is 25%~28% ammoniacal liquor, obtains mixed solution A；
Step one 2. described in ZnNO3·6H2The amount of the material of O is 0.005mol with the volume ratio of deionized water: (50mL~60mL)；
Step one 2. described in ZnNO3·6H2The amount and mass fraction of the material of O are the body of 25%~28% ammoniacal liquor Product is than being 0.005mol:(10mL~20mL)；
On one surface of the clean nickel sheet obtained during 1. Kapton Tape 3., is pasted into step one, then immerse To step one 2. in react 6h~8h in the mixed solution A that obtains, then at being 90 DEG C in temperature, carried out using distilled water after taking-up Rinse 3 times~5 times, obtain the nickel sheet of area load ZnO micron bar arrays；
2nd, the nickel sheet of the ZnO/Ni micron bar arrays of area load core shell structure is prepared：
1., by NiSO4And NH4Cl is added in deionized water, then carries out ultrasonic disperse 15min~20min, is mixed Solution B；
Step 2 1. described in NiSO4The volume ratio of amount and deionized water of material be 0.005mol:(80mL~ 120mL)；
Step 2 1. described in NH4The amount of the material of Cl is 0.001mol with the volume ratio of deionized water:(80mL~ 120mL)；
, used as working electrode, nickel sheet is used as right for the nickel sheet of the area load ZnO micron bar arrays that 2., will be obtained in step one Electrode, electro-deposition is carried out in the mixed solution B obtained in being immersed in step 2 1. by working electrode and to electrode, then will load The nickel sheet of ZnO micron bar arrays is taken out, and reuses distilled water flushing 3 times~5 times, obtains the ZnO/Ni of area load core shell structure The nickel sheet of micron bar array；
Step 2 2. described in electro-deposition be on electrochemical workstation complete, wherein current density be 2.0~ 3.0mA cm-2, electrodeposition time is 250s~350s；
3rd, the nickel sheet of the Ni/C micron bar arrays of area load core shell structure is prepared；
1., glucose is added in deionized water, then carries out ultrasonic disperse 15min~20min, obtain mixed solution C；
Step 3 1. described in the volume ratio of amount and deionized water of material of glucose be 0.2mol:(80mL~ 120mL)；
It is sub- that the nickel sheet of the ZnO/Ni micron bar arrays of the area load core shell structure that 2., will be obtained in step 2 posts polyamides The face of amine adhesive tape is fixed on slide, then is immersed in dress by the downward form of the ZnO/Ni micron bar arrays of load core shell structure In having a polytetrafluoroethylliner liner of mixed solution C, then polytetrafluoroethylliner liner is put into autoclave；
3. autoclave, is reacted into 2h~5h in the case where temperature is for 150 DEG C~200 DEG C, room temperature is cooled to, is reacted Thing；Reactant is taken out, distilled water flushing is reused 3 times~5 times, then by reactant argon gas atmosphere and temperature be 450 DEG C~ 40min~90min is heat-treated at 550 DEG C, the nickel sheet of the Ni/C micron bar arrays of area load core shell structure is obtained, it is as hollow Nickel rod/carbon ball array electrode.
Present embodiment step 3 2. in will be obtained in step 2 area load core shell structure ZnO/Ni micron bars battle array That face of the ZnO/Ni micron bar arrays of the unsupported core shell structure of nickel sheet of row is fixed on slide, is to use high temperature resistant polyamides What imines adhesive tape was fixed.
Present embodiment step 3 3. in by autoclave temperature be 150 DEG C~200 DEG C at react 2h~5h, this mistake ZnO is by the micro- harsh eating away of generation in water-heat process in journey.
The principle and advantage of present embodiment：
First, present embodiment synthesizes ZnO micron bars array and makes it vertical by the method for chemical bath deposition CBD first Length is in nickel sheet.Then the ZnO/Ni of core shell structure is prepared on ZnO micron bar arrays by the method for electrochemical deposition ED Micron bar array, then by hydro-thermal method and the method for annealing, prepare the Ni/C micron bar arrays of core shell structure.It is this hollow Nickel micrometer tube array is directly connected with collector, it is not necessary to any conductive additive, improves the energy density of battery.It is more important , in subsequent cycle performance test, with current density as 50mA/g under conditions of, the Hollow Nickel of present embodiment preparation Capacity retention can be very good after the circle of discharge and recharge 100 for rod/carbon ball array electrode；
2nd, in 50mA g-1Current density under, present embodiment prepare Hollow Nickel rod/carbon ball array electrode charging Capacity is up to 170mAh g-1；
3rd, Hollow Nickel rod/carbon ball array electrode prepared by present embodiment is remained greater than after 100 cycle periods 148mAh g-1Capacity, this shows good cycle performance, is remained above 86.8% capacity.
Present embodiment is suitable for preparing Hollow Nickel rod/carbon ball array electrode.
Specific embodiment two：Present embodiment is with the difference of specific embodiment one：Step one 2. described in ZnNO3·6H2The amount of the material of O is 0.005mol with the volume ratio of deionized water:55mL.Other steps and specific embodiment One is identical.
Specific embodiment three：One of present embodiment and specific embodiment one or two difference is：Step one 2. in Described ZnNO3·6H2The amount of the material of O is 0.005mol with the volume ratio of the ammoniacal liquor that mass fraction is 25%~28%: 15mL.Other steps are identical with specific embodiment one or two.
Specific embodiment four：One of present embodiment and specific embodiment one to three difference is：Step one 1. in The thickness of described nickel sheet is 0.15mm~0.2mm.Other steps are identical with specific embodiment one to three.
Specific embodiment five：One of present embodiment and specific embodiment one to four difference is：Step 2 1. in Described NiSO4The volume ratio of amount and deionized water of material be 0.005mol:100mL.Other steps and specific embodiment party Formula one to four is identical.
Specific embodiment six：One of present embodiment and specific embodiment one to five difference is：Step 2 1. in Described NH4The amount of the material of Cl is 0.001mol with the volume ratio of deionized water:100mL.Other steps and specific embodiment party Formula one to five is identical.
Specific embodiment seven：One of present embodiment and specific embodiment one to six difference is：Step 2 2. in Described electro-deposition is completed on electrochemical workstation, and wherein current density is 2.0~2.5mA cm-2, electrodeposition time It is 250s~300s.Other steps are identical with specific embodiment one to six.
Specific embodiment eight：One of present embodiment and specific embodiment one to seven difference is：Step 3 1. in The amount of the material of described glucose is 0.2mol with the volume ratio of deionized water:100mL.Other steps and specific embodiment One to seven is identical.
Specific embodiment nine：One of present embodiment and specific embodiment one to eight difference is：Step 3 3. in 2h~3h is reacted at being 150 DEG C~180 DEG C in temperature by autoclave, room temperature is cooled to, reactant is obtained；By reactant Take out, reuse distilled water flushing 3 times~5 times, then by reactant be 450 DEG C~500 DEG C in argon gas atmosphere and temperature at heat Reason 40min~60min, obtains the nickel sheet of the Ni/C micron bar arrays of area load core shell structure, as Hollow Nickel rod/carbon ball battle array Row electrode.Other steps are identical with specific embodiment one to eight.
Specific embodiment ten：One of present embodiment and specific embodiment one to nine difference is：Step 3 3. in 3h~5h is reacted at being 180 DEG C~200 DEG C in temperature by autoclave, room temperature is cooled to, reactant is obtained；By reactant Take out, reuse distilled water flushing 3 times~5 times, then by reactant be 500 DEG C~550 DEG C in argon gas atmosphere and temperature at heat Reason 60min~90min, obtains the nickel sheet of the Ni/C micron bar arrays of area load core shell structure, as Hollow Nickel rod/carbon ball battle array Row electrode.Other steps are identical with specific embodiment one to nine.
Beneficial effects of the present invention are verified using following examples：
Embodiment one：A kind of preparation method of Hollow Nickel rod/carbon ball array electrode, is specifically realized by the following steps：
First, the nickel sheet of area load ZnO micron bar arrays is prepared：
1. nickel sheet is cleaned by ultrasonic 4 times first by acetone, absolute ethyl alcohol is reused and nickel sheet is cleaned by ultrasonic 4 times, then will Its drying, obtains the nickel sheet of cleaning；
Step one 1. described in nickel sheet thickness be 0.2mm；
2., by ZnNO3·6H2O is added in deionized water, then carries out ultrasonic disperse 15min, and adding mass fraction is 28% ammoniacal liquor, obtains mixed solution A；
Step one 2. described in ZnNO3·6H2The amount of the material of O is 0.005mol with the volume ratio of deionized water: 55mL；
Step one 2. described in ZnNO3·6H2The amount of the material of O is with the volume ratio of the ammoniacal liquor that mass fraction is 28% 0.005mol:15mL；
On one surface of the clean nickel sheet obtained during 1. Kapton Tape 3., is pasted into step one, then immerse To step one 2. in react 7h in the mixed solution A that obtains, then at being 90 DEG C in temperature, be rinsed using distilled water after taking-up 4 times, obtain the nickel sheet of area load ZnO micron bar arrays；
2nd, the nickel sheet of the ZnO/Ni micron bar arrays of area load core shell structure is prepared：
1., by NiSO4And NH4Cl is added in deionized water, then carries out ultrasonic disperse 15min~20min, is mixed Solution B；
Step 2 1. described in NiSO4The volume ratio of amount and deionized water of material be 0.005mol:100mL；
Step 2 1. described in NH4The amount of the material of Cl is 0.001mol with the volume ratio of deionized water:100mL；
, used as working electrode, nickel sheet is used as right for the nickel sheet of the area load ZnO micron bar arrays that 2., will be obtained in step one Electrode, electro-deposition is carried out in the mixed solution B obtained in being immersed in step 2 1. by working electrode and to electrode, then will load The nickel sheet of ZnO micron bar arrays is taken out, and reuses distilled water flushing 4 times, obtains ZnO/Ni microns of area load core shell structure The nickel sheet of rod array；
Step 2 2. described in electro-deposition be on electrochemical workstation complete, wherein current density be 2.5mA cm-2, electrodeposition time is 300s；
3rd, the nickel sheet of the Ni/C micron bar arrays of area load core shell structure is prepared；
1., glucose is added in deionized water, then carries out ultrasonic disperse 15min, obtain mixed solution C；
Step 3 1. described in the volume ratio of amount and deionized water of material of glucose be 0.2mol:100mL；
It is sub- that the nickel sheet of the ZnO/Ni micron bar arrays of the area load core shell structure that 2., will be obtained in step 2 posts polyamides The face of amine adhesive tape is fixed on slide, then is soaked by the downward form of the ZnO/Ni micron bar arrays that core shell structure is loaded in nickel sheet Enter in the polytetrafluoroethylliner liner equipped with mixed solution C, then polytetrafluoroethylliner liner is put into autoclave；
3. autoclave, is reacted into 3h in the case where temperature is for 180 DEG C, room temperature is cooled to, reactant is obtained；By reactant Take out, reuse distilled water flushing 4 times, then reactant is heat-treated 60min in the case where argon gas atmosphere and temperature are for 500 DEG C, obtain The nickel sheet of the Ni/C micron bar arrays of area load core shell structure, as Hollow Nickel rod/carbon ball array electrode.
Fig. 1 is to prepare the schematic diagram of Hollow Nickel rod/carbon ball array electrode in embodiment one, and 1 is the step of embodiment one in Fig. 1 The nickel sheet of the area load ZnO micron bar arrays obtained in, 2 is the area load nucleocapsid knot obtained in the step 2 of embodiment one The nickel sheet of the ZnO/Ni micron bar arrays of structure, 3 is micro- for the Ni/C of the area load core shell structure obtained in the step 3 of embodiment one The nickel sheet of rice rod array；
Fig. 2 is ZnO micron bar arrays in the nickel sheet of the area load ZnO micron bar arrays obtained in the step one of embodiment one Amplify 5000 times of SEM figures；
Fig. 3 is ZnO micron bar arrays in the nickel sheet of the area load ZnO micron bar arrays obtained in the step one of embodiment one Amplify 10000 times of SEM figures；
Fig. 4 is in the nickel sheet of the ZnO/Ni micron bar arrays of area load core shell structure obtained in the step 2 of embodiment one The ZnO/Ni micron bars array of core shell structure amplifies 5000 times of SEM figures；
Fig. 5 is in the nickel sheet of the ZnO/Ni micron bar arrays of area load core shell structure obtained in the step 2 of embodiment one The ZnO/Ni micron bars array of core shell structure amplifies 10000 times of SEM figures；
Fig. 6 is the nickel sheet coker of the Ni/C micron bar arrays of area load core shell structure obtained in the step 3 of embodiment one The Ni/C micron bars array of shell structure amplifies 3000 times of SEM figures；
Fig. 7 is the nickel sheet coker of the Ni/C micron bar arrays of area load core shell structure obtained in the step 3 of embodiment one The Ni/C micron bars array of shell structure amplifies 8000 times of SEM figures；
Fig. 8 is single in the nickel sheet of the Ni/C micron bar arrays of area load core shell structure obtained in the step 3 of embodiment one The Ni/C micron bars array of individual rupture amplifies 8000 times of SEM figures；
Fig. 9 is the nickel sheet coker of the Ni/C micron bar arrays of area load core shell structure obtained in the step 3 of embodiment one The Ni/C micron bars array of shell structure amplifies 8000 times of TEM figures；
Figure 10 is in the nickel sheet of the Ni/C micron bar arrays of area load core shell structure obtained in the step 3 of embodiment one The Ni/C micron bar arrays of core shell structure amplify 100,000 times of TEM figures；
Figure 11 is in the nickel sheet of the Ni/C micron bar arrays of area load core shell structure obtained in the step 3 of embodiment one The Ni/C micron bar arrays of core shell structure amplify 1,000,000 times of HRTEM figures；
Figure 12 is Raman spectrogram, and 1 is the Raman curve of the ZnO/Ni micron bar arrays of core shell structure in Figure 12, and 2 is core The Raman curve of the Ni/C micron bar arrays of shell structure, A is the absworption peak of ZnO, and D is the SP3 keys of Nano carbon balls, and G is carbon nanometer The SP2 keys of ball；
Figure 13 is XRD curves, and 1 is the XRD curves of the ZnO/Ni micron bar arrays of core shell structure in Figure 13, and 2 is nucleocapsid knot The XRD curves of the Ni/C micron bar arrays of structure, " ◆ " is the diffraction maximum of ZnO；
Figure 14 is the cyclic curve of Hollow Nickel rod/carbon ball array electrode that the step 3 of embodiment one is obtained, and " " is charging, "○" is electric discharge；
Figure 15 is the curve of double curvature of Hollow Nickel rod/carbon ball array electrode that the step 3 of embodiment one is obtained, and A is electricity in Figure 15 Current density is 50mAg-1Under curve of double curvature, B be current density be 100mAg-1Under curve of double curvature, C is for current density 200mAg-1Under curve of double curvature, D be current density be 500mAg-1Under curve of double curvature, E be current density be 1000mAg-1Under Curve of double curvature, F be current density be 2000mAg-1Under curve of double curvature, G be current density be 50mAg-1Under multiplying power it is bent Line.
As can be seen from Figure 2, nickel sheet is completely covered by ZnO micron bar arrays.
As can be seen from Figure 3, the length for growing ZnO in the ZnO micron bar arrays in nickel sheet is about 20 microns, ZnO micron bars Diameter is about 500 nanometers~600 nanometers.ZnO micron bars are the mono-crystalline structures of typical six prismatics, and almost completely vertical It is grown in nickel substrate surface.
Knowable to Fig. 4 and Fig. 5, array structure is still kept after each ZnO/Ni micron bar electroplating process.
Knowable to Fig. 6 and Fig. 7, ZnO micron bars are fully wrapped around by carbon nanometer micro ball, the diameter of Ni nanotubes/C nano microballoon About 2 μm.
As it can be observed in the picture that being a micron tube for fracture, it has a hollow micron tubular construction.Further illustrate ZnO micro- Rice rod is dissolved in hydrothermal reaction process, and its tubular structure keeps good.
Knowable to Fig. 9 and Figure 10, Ni nanotubes/C nano microballoon core shell structure is by carbosphere after hydro-thermal method treatment sample The uniform parcel of layer, and surface becomes coarse after parcel.ZnO micron bars are dissolved in hydrothermal reaction process, and its structure Direction with array remains intact.
Can also be knowable to Fig. 9 and Figure 10, Nano carbon balls yardstick is than more uniform, and to completely cover nickel micron bar Surface, and its nickel micron bar structure by complete in store, can also be clearly seen that hollow structure, preferably prove The core shell structure array structure of hollow nickel micron bar/Nano carbon balls.
As can be seen from Figure 11, Nano carbon balls possess good spherical structure, and diameter is between 50nm~200nm.Meanwhile, As can be seen from Figure 11, this Nano carbon balls do not have lattice fringe, are the structures of amorphous carbon, and its outward appearance is spherical complete.
Figure 12 is Raman spectrogram, and 1 is the Raman curve of the ZnO/Ni micron bar arrays of core shell structure in Figure 12, and 2 is core The Raman curve of the Ni/C micron bar arrays of shell structure；
As can be seen from Figure 12, by the ZnO/Ni micron bars after chemical bath deposition (CBD) and electrochemical deposition (ED) treatment As can be seen that there are the Raman peaks of typical ZnO in this sample in Raman spectrum, but in the micro- of Ni/C nanosphere nucleocapsids The Raman peaks that this ZnO can be obtained in the Raman spectrum of rice rod disappear, and show the nucleocapsid knot of Hollow Nickel micron bar/Nano carbon balls Structure array is thoroughly etched away in preparation process by the template of those ZnO micron bars after hydro-thermal process.Two strong peaks are located at 1347cm-1D peaks and 1597cm-1G peaks, be typical carbon Raman peaks.Result shows, from ZnO/Ni and Ni/C nanometers of ball ZnO micron bars in the core shell structure array of Hollow Nickel micron bar/Nano carbon balls are observed that in the Raman spectrum of shell micron bar It is etched away, while being supported by water-heat process carbon ball；For the SP3 keys of Nano carbon balls, (lattice in carbocyclic ring lacks D in Figure 12 Fall into the Raman absorption peak produced with unordered induction), G is SP2 keys (all SP in carbocyclic ring or long-chain of Nano carbon balls2Atom pair Extensional motion produce Raman absorption peak), be all the Raman absorption peak of typical carbon ball；
Figure 13 is XRD curves, and 1 is the XRD curves of the ZnO/Ni micron bar arrays of core shell structure in Figure 13, and 2 is nucleocapsid knot The XRD curves of the Ni/C micron bar arrays of structure；
As can be seen from Figure 13, there is the nickel peak of peak intensity very high after electro-deposition can be seen in two collection of illustrative plates, may certify that out The presence of nickel dam after electro-deposition.The diffraction maximum for obtaining ZnO from the XRD spectrum of ZnO/Ni nanosphere nucleocapsid micron bars simultaneously goes out respectively Present 32.1 °, 34.8 °, 36.8 °, 47.1 °, 57.2 °, 62.8 °, 64.7 °, 67.2 ° and 68.6 ° of position, can correspond to (100), the crystal face of (022), (101), (102), (110), (103), (200), (112) and (201), reference standard spectrogram (JCPDS No.36-1451) understands the ZnO crystal for hexagon crystal formation.From the XRD diffraction of the micron bar of Ni/C nanosphere nucleocapsids In collection of illustrative plates, it can be seen that the diffraction maximum of ZnO disappears, the template for also demonstrating this ZnO micron bar from Raman collection of illustrative plates above disappears Lose.Contrast Raman shows with XRD diffracting spectrum results, ZnO microns in the core shell structure array of Hollow Nickel micron bar/Nano carbon balls Rod is etched away, while by the presence of carbon ball after water-heat process.
As can be seen from Figure 14, the Hollow Nickel rod/carbon ball array electrode for being obtained in the step 3 of embodiment one is in 100 cycle periods 148mAh g are still kept afterwards-1Capacity, this shows good cycle performance, keeps 86.8% capacity.Nano carbon balls are good Electrical conductivity improve the speed that transports of ion, improve the cycle performance of electrode.In the core shell structure of nickel micron bar/Nano carbon balls There is sufficiently large space structure, the Hollow Nickel in cyclic process that this structure can be accommodated between the micron bar of array electrode The Volume Changes of rod/carbon ball array electrode, so as to improve the stability of circulation.
From figure 15, it can be known that in 50mA g-1Current density under Hollow Nickel rod/carbon ball array for obtaining of the step 3 of embodiment one The charging capacity of electrode is up to 170mAh g-1, in 2000mA g-1Current density under the electrode charging hold be 27mAh g-1, It is then return to 50mA g-1Current density after its charging capacity be changed into 123mA g-1。
Hollow Nickel rod/carbon ball array electrode that the step 3 of embodiment one is obtained has excellent high rate performance, is due to this The structure of micron bar array has larger specific surface area, and large-specific surface area nano fibre structure increases electrolyte with carbon ball Contact area, shortens the transmission path of lithium ion, and reduces the Volume Changes caused in electrochemical reaction process, so that Improve the lithium storage capacity of the electrode.

Claims (10)

1. a kind of preparation method of Hollow Nickel rod/carbon ball array electrode, it is characterised in that the method is specifically complete according to the following steps Into：
First, the nickel sheet of area load ZnO micron bar arrays is prepared：
1. nickel sheet is cleaned by ultrasonic 3 times~5 times first by acetone, absolute ethyl alcohol is reused and 3 times~5 is cleaned by ultrasonic to nickel sheet It is secondary, then be baked to, obtain the nickel sheet of cleaning；
Step one 1. described in nickel sheet thickness be 0.15mm~0.5mm；
2., by ZnNO3·6H2O is added in deionized water, then carries out ultrasonic disperse 15min~20min, adds mass fraction It is 25%~28% ammoniacal liquor, obtains mixed solution A；
Step one 2. described in ZnNO3·6H2The amount of the material of O is 0.005mol with the volume ratio of deionized water:(50mL~ 60mL)；
Step one 2. described in ZnNO3·6H2The amount and mass fraction of the material of O are the volume ratio of 25%~28% ammoniacal liquor It is 0.005mol:(10mL~20mL)；
On one surface of the clean nickel sheet obtained during 1. Kapton Tape 3., is pasted into step one, then it is immersed in step Rapid one 2. in react 6h~8h in the mixed solution A that obtains, then at being 90 DEG C in temperature, be rinsed using distilled water after taking-up 3 times~5 times, obtain the nickel sheet of area load ZnO micron bar arrays；
2nd, the nickel sheet of the ZnO/Ni micron bar arrays of area load core shell structure is prepared：
1., by NiSO4And NH4Cl is added in deionized water, then carries out ultrasonic disperse 15min~20min, obtains mixed solution B；
Step 2 1. described in NiSO4The volume ratio of amount and deionized water of material be 0.005mol:(80mL~120mL)；
Step 2 1. described in NH4The amount of the material of Cl is 0.001mol with the volume ratio of deionized water:(80mL~120mL)；
, used as working electrode, nickel sheet is used as to electricity for the nickel sheet of the area load ZnO micron bar arrays that 2., will be obtained in step one Pole, electro-deposition is carried out in the mixed solution B obtained in being immersed in step 2 1. by working electrode and to electrode, then will load The nickel sheet of ZnO micron bar arrays is taken out, and reuses distilled water flushing 3 times~5 times, obtains the ZnO/Ni of area load core shell structure The nickel sheet of micron bar array；
Step 2 2. described in electro-deposition be on electrochemical workstation complete, wherein current density be 2.0~3.0mA cm-2, electrodeposition time is 250s~350s；
3rd, the nickel sheet of the Ni/C micron bar arrays of area load core shell structure is prepared；
1., glucose is added in deionized water, then carries out ultrasonic disperse 15min~20min, obtain mixed solution C；
Step 3 1. described in the volume ratio of amount and deionized water of material of glucose be 0.2mol:(80mL~120mL)；
The nickel sheet of the ZnO/Ni micron bar arrays of the area load core shell structure that 2., will be obtained in step 2 posts polyimides glue The face of band is fixed on slide, then is immersed in equipped with mixed by the downward form of the ZnO/Ni micron bar arrays containing core shell structure In the polytetrafluoroethylliner liner of conjunction solution C, then polytetrafluoroethylliner liner is put into autoclave；
3. autoclave, is reacted into 2h~5h in the case where temperature is for 150 DEG C~200 DEG C, room temperature is cooled to, reactant is obtained； Reactant is taken out, distilled water flushing is reused 3 times~5 times, then in argon gas atmosphere and temperature is 450 DEG C~550 by reactant 40min~90min is heat-treated at DEG C, the nickel sheet of the Ni/C micron bar arrays of area load core shell structure, as Hollow Nickel is obtained Rod/carbon ball array electrode.
2. a kind of preparation method of Hollow Nickel rod/carbon ball array electrode according to claim 1, it is characterised in that step one 2. the ZnNO described in3·6H2The amount of the material of O is 0.005mol with the volume ratio of deionized water:55mL.
3. a kind of preparation method of Hollow Nickel rod/carbon ball array electrode according to claim 1, it is characterised in that step one 2. the ZnNO described in3·6H2The amount of the material of O is 0.005mol with the volume ratio of the ammoniacal liquor that mass fraction is 25%~28%: 15mL。
4. a kind of preparation method of Hollow Nickel rod/carbon ball array electrode according to claim 1, it is characterised in that step one The thickness of the nickel sheet described in 1. is 0.15mm~0.2mm.
5. a kind of preparation method of Hollow Nickel rod/carbon ball array electrode according to claim 1, it is characterised in that step 2 1. the NiSO described in4The volume ratio of amount and deionized water of material be 0.005mol:100mL.
6. a kind of preparation method of Hollow Nickel rod/carbon ball array electrode according to claim 1, it is characterised in that step 2 1. the NH described in4The amount of the material of Cl is 0.001mol with the volume ratio of deionized water:100mL.
7. a kind of preparation method of Hollow Nickel rod/carbon ball array electrode according to claim 1, it is characterised in that step 2 2. the electro-deposition described in is completed on electrochemical workstation, and wherein current density is 2.0~2.5mA cm-2, electro-deposition Time is 250s~300s.
8. a kind of preparation method of Hollow Nickel rod/carbon ball array electrode according to claim 1, it is characterised in that step 3 The amount of the material of the glucose described in 1. is 0.2mol with the volume ratio of deionized water:100mL.
9. a kind of preparation method of Hollow Nickel rod/carbon ball array electrode according to claim 1, it is characterised in that step 3 3. autoclave is reacted into 2h~3h in the case where temperature is for 150 DEG C~180 DEG C in, room temperature is cooled to, reactant is obtained；Will be anti- Answer thing to take out, reuse distilled water flushing 3 times~5 times, then by reactant in the case where argon gas atmosphere and temperature are for 450 DEG C~500 DEG C Heat treatment 40min~60min, the as nickel sheet of the Ni/C micron bar arrays for obtaining containing core shell structure in surface, Hollow Nickel rod/carbon Ball array electrode.
10. a kind of preparation method of Hollow Nickel rod/carbon ball array electrode according to claim 1, it is characterised in that step Three 3. in by autoclave temperature be 180 DEG C~200 DEG C at react 3h~5h, be cooled to room temperature, obtain reactant；Will Reactant takes out, and reuses distilled water flushing 3 times~5 times, then in argon gas atmosphere and temperature is 500 DEG C~550 DEG C by reactant Lower heat treatment 60min~90min, obtains the nickel sheet of the Ni/C micron bar arrays of area load core shell structure, as Hollow Nickel rod/ Carbon ball array electrode.
CN201710193108.0A 2017-03-28 2017-03-28 A kind of preparation method of Hollow Nickel rod/carbon ball array electrode Pending CN106876658A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110492076A (en) * 2019-08-22 2019-11-22 河南师范大学 A kind of preparation method of the porous hexagonal metallic oxide nano-slice composite material of two dimension and its application in kalium ion battery
AU2020201235B1 (en) * 2019-10-23 2020-08-06 Hubei University Self-supporting nickel nanotubes on nickel foam as electrode materials for supercapacitors and preparation method thereof
CN111740095A (en) * 2020-07-01 2020-10-02 湖北大学 Carbon microsphere coated zinc oxide nanosheet material and preparation method and application thereof
CN113026072A (en) * 2019-12-25 2021-06-25 南京理工大学 Method for preparing metal oxide nanotube array by combining template and pulse method

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* Cited by examiner, † Cited by third party
Title
XINHUI XIA ET AL.: "Novel Metal@Carbon Spheres Core–Shell Arrays by Controlled Self-Assembly of Carbon Nanospheres:A Stable and Flexible Supercapacitor Electrode", 《ADV. ENERGY MATER.》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110492076A (en) * 2019-08-22 2019-11-22 河南师范大学 A kind of preparation method of the porous hexagonal metallic oxide nano-slice composite material of two dimension and its application in kalium ion battery
CN110492076B (en) * 2019-08-22 2022-04-05 河南师范大学 Preparation method of two-dimensional porous hexagonal metal oxide nanosheet composite material and application of composite material in potassium ion battery
AU2020201235B1 (en) * 2019-10-23 2020-08-06 Hubei University Self-supporting nickel nanotubes on nickel foam as electrode materials for supercapacitors and preparation method thereof
CN113026072A (en) * 2019-12-25 2021-06-25 南京理工大学 Method for preparing metal oxide nanotube array by combining template and pulse method
CN113026072B (en) * 2019-12-25 2022-12-13 南京理工大学 Method for preparing metal oxide nanotube array by combining template and pulse method
CN111740095A (en) * 2020-07-01 2020-10-02 湖北大学 Carbon microsphere coated zinc oxide nanosheet material and preparation method and application thereof
CN111740095B (en) * 2020-07-01 2021-12-21 湖北大学 Carbon microsphere coated zinc oxide nanosheet material and preparation method and application thereof

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