CN107204450A - The preparation method and applications of nickel oxide nanoparticle/carbon nanometer helmet composite (NiO/CNHs) - Google Patents
The preparation method and applications of nickel oxide nanoparticle/carbon nanometer helmet composite (NiO/CNHs) Download PDFInfo
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- H—ELECTRICITY
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- 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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- 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
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Abstract
The present invention relates to a kind of preparation method of nickel oxide nanoparticle/carbon nanometer helmet composite (NiO/CNHs) and its application in lithium ion battery.The preparation process of the composite is as follows：A, preparation SiO2Nanosphere；B, in SiO2Phenolic coating (RF) formation RF/SiO is covered on ball2；C, with hydro-thermal method in RF/SiO2Upper preparation Ni (OH)2；D, by prepared Ni (OH)2/RF/SiO2Annealing makes Ni (OH) in an ar atmosphere2NiO is converted into while making RF be carbonized, then with NaOH solution by SiO2Thoroughly corrosion obtains NiO/CNHs.As the negative material of lithium ion battery, NiO/CNHs is in 0.2A g‑1The capacity of the circle of circulation 100 is up to 1768mAh g under current density‑1；In 5A g‑1The capacity of the circle of circulation 1500 is 424mAh g under current density‑1；In 10A g‑1Capacity under current density is 453mAh g‑1.The present invention provides new thinking to research and develop the lithium ion battery of excellent combination property.
Description
Technical field：
The present invention relates to the preparation method of nickel oxide nanoparticle/carbon nanometer helmet composite (NiO/CNHs) and its work
For the application of lithium ion battery negative material.
Background technology：
The energy storage equipment of clean and effective plays most important in terms of reply energy crisis, reduction greenhouse gas emission
Effect.Lithium ion battery (LIBs) is current first choice, especially for portable electric appts.Its significant challenge faced
It is to develop high reversible specific capacity, cyclical stability and the excellent electrode material of high rate performance.It is used as commercial li-ion battery
Negative material, the theoretical capacity of graphite is very low, only 372mAh g-1, this does not reach the requirement of large-scale application much, such as
New-energy automobile.Recently, transition metal oxide with very high theoretical capacity because being considered as LIBs negative materials
One kind selection.However, chemical property of the transition metal oxide as NiO in lithium ion battery is limited to two sides
Face：One is Li in charge and discharge process+Insertion/deintercalation makes its Volume Changes huge；In addition, the electric conductivity of themselves is excessively poor.
In order to solve the two problems, scientific research personnel has carried out many trials, for example：By NiO and the elastic fluid of high conductivity,
Such as CNT, graphene, carbon fiber, mesoporous carbon spheres etc. are combined；Prepare NiO hollow-core constructions；Synthesize extra small NiO nanocrystalline etc.
Deng.Recently, Lou Xiongwen teaches seminar and devises hollow bowl-shape hetero-junctions NiO nanoscale twins being grown on carbon nano-particle
Structure.This structure combines the advantage of hollow-core construction and high conductivity medium, and improves the stacking density of active material.Cause
This, it shows excellent electrochemical properties in lithium ion battery, such as in 0.2Ag-1Current density under circulation 150 circle after
Reversible capacity is 950mAh g-1.But this structure still suffers from some problems：(1) inwall of its hollow Nano carbon particle not by
Utilize；(2) can only be between particle NiO-NiO contact, increase internal resistance；(3) presence of closing space is unfavorable for electrolyte
Fully infiltrate active material.
The content of the invention：
The purpose of the present invention is to prepare nickel oxide nanoparticle/carbon nanometer helmet composite (NiO/CNHs) and be applied to
Lithium ion battery.Unique open helmet structure makes NiO/CNHs heterojunction materials take full advantage of the inwall of carbon skeleton, is
Li+Insertion/deintercalation provides a large amount of extra avtive spots, and can effectively buffer NiO bodies huge in charge/discharge cycle
Product change.In addition, being contacts of the NiO with carbon between particle, internal resistance is greatly reduced.In addition, porous carbon skeleton is provided efficiently
Electrolyte diffusion path.Therefore, NiO/CNHs heterojunction electrodes show excellent chemical property in lithium ion battery.
The above-mentioned purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of the composite (NiO/CNHs) of nickel oxide nanoparticle/and the carbon nanometer helmet, including with
Lower step：
A, by improvedMethod synthesizes a diameter of 300~400nm SiO2Nanosphere：By the different of 60~65ml
Propyl alcohol is mixed evenly with 20~24ml ultra-pure waters and 10~15ml ammoniacal liquor, adds 0.5~0.8ml tetraethyl orthosilicates, room temperature
30~60min is stirred, then 4~6ml tetraethyl orthosilicates are added dropwise, product centrifugation is used water and alcohol by 30~40 DEG C of 2~3h of stirring again
Cleaning 3~5 times, 70~80 DEG C of 10~12h of vacuum drying；
B, by sol-gal process in SiO2Ball surface coating phenolic resin obtains RF/SiO2Nanosphere：Take 0.8~1g
SiO2Ultrasonic disperse Jia 2~2.4g cetyl trimethyl brominations successively in 65~70ml water and 25~3 alcohol mixeding liquids
20~30min is stirred at room temperature in ammonium, 0.3~0.4g resorcinols, 0.1~0.2ml ammoniacal liquor, then Jia 0.3~0.5ml formalins,
30~40 DEG C of 7~8h of stirring, by product centrifugation again with water and alcohol washes 3~5 times, 70~80 DEG C of 10~12h of vacuum drying；
C, pass through hydro-thermal method prepare Ni (OH)2/RF/SiO2Nanosphere：By 0.8~1g RF/SiO2Nanosphere, 1.4~
1.5g Nickelous nitrate hexahydrates, the mixing of 1.3~1.5g hexamethylene tetramines and 10~15ml ethanol and 20~30ml ultra-pure waters
Thing is added in the stainless steel autoclave with polytetrafluoroethyllining lining, and sealed reactor is put into 100~120 DEG C of electricity
10~12h is incubated in baking oven, by product by being collected by centrifugation, 70~80 DEG C of 10~12h of vacuum drying；
D, by prepared Ni (OH)2/RF/SiO2Nanosphere anneals 2 in tube furnace Ar atmosphere under the conditions of 550~600 DEG C
~3h, be cooled to after 320~350 DEG C again blowing air cooling, after cooling by product 60 in 2~3M sodium hydrate aqueous solution~
70 DEG C of 24~48h of immersion, product is centrifuged and cleaned with water 3~5 times, 70~80 DEG C of 10~12h of vacuum drying.
In step a SiO is controlled by adjusting the ratio of isopropanol, ultra-pure water and ammoniacal liquor2The size of ball.
Ni (OH) is prepared in step c2When, Ni (OH) is controlled by controlling hydrothermal temperature2Pattern.
NiO pattern obtained by being controlled in step d as annealing temperature.
The nickel oxide nanoparticle that above-mentioned preparation method is obtained/carbon nanometer helmet composite (NiO/CNHs), it is made
Electro-chemical test is carried out for lithium ion battery electrode material, is comprised the following steps：
It is prepared by a, working electrode：First by active material, acetylene black and binding agent Kynoar are according to 7:2:1 ratio exists
It is coated on after being mixed evenly in 1-METHYLPYRROLIDONE on copper foil, then 10~12h of vacuum drying at 80~120 DEG C；
B, lithium ion battery assembling：Using active material NiO/CNHs as working electrode, lithium piece is as to electrode/reference electricity
Pole, barrier film is the films of Celgard 2500, and electrolyte is 1M LiPF6It is 1 to be dissolved in volume ratio:1:1 ethylene carbonate, carbonic acid
In the mixed liquor of dimethyl ester and methyl ethyl carbonate, CR2016 type button cells, gloves are assembled into the glove box full of argon gas
The water oxygen value of case is respectively [O2]<1ppm,[H2O]<1ppm；
C, cyclic voltammetry are carried out with IVIUM electrochemical workstations, and it is 0.1~0.2mV/s, test voltage to sweep speed
Scope is 0.01-3.0V；
It is 100kHz to 10mHz that d, electrochemical impedance, which test tangible room temperature lower frequency range,；
E, constant current charge-discharge loop test are carried out using LAND CT2001A between voltage range 0.01-3.0V.
The solution have the advantages that：
Nickel oxide nanoparticle produced by the present invention/carbon nanometer helmet composite (NiO/CNHs) has high conductivity,
Bigger serface and fast electrochemical reaction speed, high power capacity is shown as the negative material of lithium ion battery, the long-life and
Excellent multiplying power discharging property.
Brief description of the drawings：
High rate performance figure of the NiO/CNHs composites in lithium ion battery in Fig. 1, the embodiment of the present invention.
The flow chart of NiO/CNHs composites is prepared in Fig. 2, the embodiment of the present invention.
The SiO prepared in Fig. 3, the embodiment of the present invention2Ball template SEM schemes.
The RF/SiO prepared in Fig. 4, the embodiment of the present invention2SEM schemes.
The NiO/C/SiO prepared in Fig. 5, the embodiment of the present invention2SEM schemes.
NiO/C/SiO in Fig. 6, the embodiment of the present invention2TEM schemes.
The NiO/CNHs composites SEM figures prepared in Fig. 7, the embodiment of the present invention.
The NiO/CNHs composites SEM figures prepared in Fig. 8, the embodiment of the present invention.
The NiO/CNHs composites SEM figures prepared in Fig. 9, the embodiment of the present invention.
Hollow carbon sphere SEM schemes in Figure 10, the embodiment of the present invention.
NiO/CNHs composites and NiO/C/SiO in Figure 11, the embodiment of the present invention2Material is in freshly prepd lithium-ion electric
Pond middle impedance comparison diagram, illustration is equivalent circuit diagram.
NiO/CNHs composites XRD in Figure 12, the embodiment of the present invention.
NiO/CNHs composites Raman curve maps in Figure 13, the embodiment of the present invention
NiO/CNHs composites N in Figure 14, the embodiment of the present invention2Suction/desorption curve figure, wherein illustration shows basis
The pore-size distribution for the sample that adsorption curve is obtained with Barrett-Joyer-Halenda (BJH) method.
NiO/CNHs composites thermogravimetric curve figure in Figure 15, the embodiment of the present invention.
NiO/CNHs composites TEM schemes in Figure 16, the embodiment of the present invention.
NiO/CNHs composites TEM schemes in Figure 17, the embodiment of the present invention.
CNHs disperses discharge and recharge stress model figure in Figure 18, the embodiment of the present invention.
NiO/CNHs composites TEM schemes in Figure 19, the embodiment of the present invention, and illustration is distributed for NiO nanoparticle sizes.
NiO/CNHs composites HRTEM schemes in Figure 20, the embodiment of the present invention.
NiO/CNHs composites HRTEM schemes in Figure 21, the embodiment of the present invention.
Cyclic voltammetry curve figure in Figure 22, the embodiment of the present invention in NiO/CNHs composite electrodes lithium ion battery,
Sweep speed is 0.2mV s-1。
The 0.2Ag in lithium ion battery of NiO/CNHs composite electrodes in Figure 23, the embodiment of the present invention-1Discharge and recharge is bent
Line chart.
The 0.2Ag in lithium ion battery of NiO/CNHs composite electrodes in Figure 24, the embodiment of the present invention-1Cycle performance
With coulombic efficiency curve map.
NiO/CNHs composites are in lithium ion battery moderate multiplying factor performance and other NiO bases in Figure 25, the embodiment of the present invention
Hollow-core construction electrode pair ratio.
The electronics and Li of NiO/CNHs composites in Figure 26, the embodiment of the present invention+Spread schematic diagram.
The 5Ag in lithium ion battery of NiO/CNHs composite electrodes in Figure 27, the embodiment of the present invention-1Cycle performance with
Coulombic efficiency curve map.
NiO/CNHs composites are recycled to the 250th circle and the 500th in lithium ion battery in Figure 28, the embodiment of the present invention
The impedance contrast figure of circle.
Embodiment
The particular content and embodiment of the present invention, but the embodiment are further illustrated with reference to embodiment
Only implement one in the present invention, it is impossible to constitute the restriction to technical solution of the present invention.
Embodiment
Preparation process and step in the present embodiment is as follows：
(1) by improvingMethod methods synthesize a diameter of 300nm SiO2Nanosphere：By 63.3ml isopropanol
It is mixed evenly with 23.5ml ultra-pure waters and 13ml ammoniacal liquor, adds 0.6ml tetraethyl orthosilicates, 60min is stirred at room temperature, then be added dropwise
5ml tetraethyl orthosilicates, 35 DEG C of stirring 2h, by product centrifugation again with water and alcohol washes 3 times, 70 DEG C of vacuum drying 10h；
(2) by sol-gal process in SiO2Ball surface coating phenolic resin obtains RF/SiO2Nanosphere：Take 1g SiO2It is super
Sound is scattered in 70ml water and 28ml alcohol mixeding liquid, and 2.3g cetyl trimethylammonium bromides, 0.35g isophthalic are added successively
Diphenol, 0.11ml ammoniacal liquor is stirred at room temperature 30min, then adds 0.5ml formalins, 35 DEG C of stirring 8h, by product centrifugation again with water and
Alcohol washes 3 times, 70 DEG C of vacuum drying 10h；
(3) Ni (OH) is prepared by hydro-thermal method2/RF/SiO2Nanosphere：By 1g RF/SiO2Nanosphere, 1.45g six is hydrated
Nickel nitrate, 1.4g hexamethylene tetramines, the mixture of 25ml ultra-pure water 10ml ethanol is added to polytetrafluoroethyllining lining
Stainless steel autoclave in；Sealed reactor is put into 100 DEG C of electric dry ovens and is incubated 10h, product is received by centrifuging
Collection, 70 DEG C of vacuum drying 10h；
(4) by prepared Ni (OH)2/RF/SiO2Nanosphere is warming up to 600 DEG C in tube furnace Ar atmosphere with 5 DEG C/min
Under the conditions of anneal 2h, blowing air cooling is cooled to after 350 DEG C again, after cooling by product 70 DEG C in 3M sodium hydrate aqueous solution
48h is soaked, product is centrifuged and cleaned with water 3 times, 70 DEG C of vacuum drying 10h.
(5) nickel oxide nanoparticle that above-mentioned preparation method is obtained/carbon nanometer helmet composite (NiO/CNHs), its
Electro-chemical test is carried out as electrode material, is comprised the following steps：
It is prepared by a, working electrode：First by active material (NiO/CNHs) 0.14g, acetylene black 0.4g and binding agent polyvinylidene fluoride
Alkene 0.2g is coated on copper foil after being mixed evenly in 1-METHYLPYRROLIDONE, then is dried in vacuo 10h at 100 DEG C；
B, lithium ion battery assembling：Using active material NiO/CNHs as working electrode, lithium piece is as to electrode/reference electricity
Pole, barrier film is the films of Celgard 2500, and electrolyte is 1M LiPF6It is 1 to be dissolved in volume ratio:1:1 ethylene carbonate, carbonic acid
In the mixed liquor of dimethyl ester and methyl ethyl carbonate, CR2016 type button cells, gloves are assembled into the glove box full of argon gas
The water oxygen value of case is respectively [O2]<1ppm,[H2O]<1ppm；
C, cyclic voltammetry are carried out with IVIUM electrochemical workstations, and it is 0.2mV/s, test voltage scope to sweep speed
For 0.01-3.0V；
D, electrochemical impedance test condition are that frequency range is 100kHz to 10mHz at room temperature；
E, constant current charge-discharge loop test are carried out using LAND CT2001A between voltage range 0.01-3.0V.
The pattern and structural characterization of nickel oxide nanoparticle/carbon nanometer helmet composite (NiO/CNHs)：
The process for preparing NiO/CNHs is as shown in Figure 2.We are characterized every in preparation process by scanning nuclear microprobe
The pattern of one step product.Fig. 3 is by improvingThe SiO that method is obtained2Template ball.Then resorcinol and formaldehyde are utilized
Polymerization, in SiO under the regulation and control of cationicsurfactants2Ball surface coats novolac resin layer, obtains RF/SiO2,
Referring to Fig. 4.The RF/SiO in this building-up process2Inner surface form Si-O-C chemical bonds, it is ensured that RF layers are brought into close contact SiO2
Ball.Afterwards, by hydro-thermal method in RF/SiO2Surface in situ growth Ni (OH)2, re-annealing obtains NiO/C/SiO2, referring to Fig. 5 and
Fig. 6.Finally, by NiO/C/SiO2NiO/CNHs heterojunction structures are obtained after continuing vigorous stirring corrosion in NaOH solution,
Referring to Fig. 7-Fig. 9.As far as we know, this is to synthesize this unique helmet-like structure first.Its Forming Mechanism is as follows：Removing
SiO2During, Si-O-C chemical bonds are destroyed, and result in the reduction of inner surface tension force.Therefore, the pressure effect produced in NiO
Lower carbon shell is shunk.As shrinkage degree becomes big, highly porous carbon skeleton can not continue support hollow-core construction and most cut off
Split to form CNHs.By contrast, acted on without NiO, the hollow carbon sphere of damaged hole, ginseng are can be only formed under same etching condition
See Figure 10.It is highly 260-300nm from the visible NiO/CNHs of Fig. 7-Fig. 9 a diameter of 400-600nm.And in Fig. 8 and Fig. 9
The CNHs of middle reflection accumulation mode has been obviously improved the bulk density of electrode material compared to hollow ball structure, improves full battery
Volume energy density.This accumulation mode also causes NiO nano particles to be in contact with CNHs, with preferable conductance property.
This point is in NiO/CNHs and NiO/C/SiO2In EIS test results (referring to Figure 11) of the ball in freshly prepd lithium ion battery
Confirmation is arrived.Equivalent circuit diagram fitting result in Figure 11 illustrations, NiO/CNHs electrodes have smaller electrode/electrolyte
Resistance RelSmaller charge transfer resistance Rct.The XRD spectrum of NiO/CNHs composites is as shown in figure 12, wherein 22.6 °
Broad peak represents the architectural feature of amorphous carbon, and the center of area is corresponded to respectively in 36.9 °, 43.4 °, 62.9 °, 75.6 ° and 79.1 ° diffraction maximums
Cubic structure NiO (111), (200), (220), (311) and (222) crystal face.Figure 13 is the Raman of NiO/CNHs composites
Spectrogram, wherein in 1069 and 526cm-1Characteristic peak it is related to NiO.In addition, in 1353 and 1598cm-1The characteristic peak at place point
The D bands and G bands of carbon material have not been corresponded to.By calculating, its intensity contrast ID/IG=0.379, show wherein there is abundant defect
And room.Figure 14 is N2Suction/desorption curve, characterizes CNHs porosity characteristic, and its BET specific surface area is 121.21m2g-1.In figure
As can be seen that CNHs most of hole size is both less than 5nm in 14 illustrations.By thermogravimetric analysis (TGA) it can be seen that NiO is compound
Content in material is 85wt% (referring to Figure 15).Wherein, thermogravimetric curve can be attributed to moisture in first 200 DEG C of mass loss
Volatilization, two other is attributable to portion of residual RF in the obvious mass loss of 200~400 DEG C and 400~600 DEG C temperature sections
The decomposition of functional group and the burning of carbon skeleton.NiO/CNHs pattern is further characterized by transmission electron microscope.From Figure 16 and figure
The NiO/CNHs of 17 visible helmet structures.Compared with bowl structure, open helmet structure takes full advantage of carbon shell inwall, can
For Li+Insertion/deintercalation provides extra avtive spot to lift specific capacity.In addition, as shown in figure 18, NiO is in discharge and recharge
The stress produced in journey can effectively be disperseed by the carbon nanometer helmet, so as to enhance the stability of electrode.In TEM Figure 19, NiO
Nano particle is uniformly fixed to CNHs surface, and size is respectively less than 10nm.Figure 19 illustrations divide for the size of NiO nano particles
Cloth.CNHs large surface/volume ratio characteristic allows extra small NiO nano particles above fully to be infiltrated by electrolyte, simultaneously
There is provided a large amount of electro-chemical activity positions and ultrashort ion diffusion length.Can from Figure 20 and 21 high-resolution TEM electromicroscopic photographs
See extra small NiO nano particles interplanar distance be 0.209nm and 0.241nm, corresponded to respectively FCC configuration NiO (200) and
(111) crystal face.The fully wrapped around NiO nano particles of amorphous carbon are also will become apparent from from figure, show to have between them good
With reference to.
At ambient temperature, the Electrochemical Characterization of NiO/CNHs composites：
Figure 22 is the NiO/CNHs electrodes cyclic voltammetry curve figure that first five is enclosed in lithium ion battery, and it is 0.2mV that it, which sweeps speed,
s-1, potential range is 0.01-3.0V (vs.Li+/Li).During first circle cathodic scan, 0.44V strong peak corresponded to NiO to
Ni changes and forms Li2The formation of O reduction reaction and irreversible solid electrolyte interface film (SEI films).After second circle, this
Individual negative electrode peak is offset to 0.95V and intensity is decreased obviously, and shows that first circle forms stable SEI films.CV curves third and fourth,
Five circles are essentially coincided with the second circle, indicate its good cyclical stability.In addition, the sun in the CV curves of NiO/CNHs electrodes
Pole part changes less in cyclic process, 1.4V and 2.25V anode peak represent respectively the decomposed and Ni of SEI films to
NiO conversion process.Figure 23 is NiO/CNHs electrodes in 0.2Ag-1The constant current charge-discharge of the 1st, 2,50 circle is bent under current density
Line.Its initial discharge capacity is 1876mAh g-1, higher than the 1513mAh g of bowl shaped structure-1.The capacity point of 2nd circle and the 50th circle
1755mAh g are not remained-1With 1769mAh g-1.This high power capacity can be attributed to the reversible decomposition in part and the surface of SEI films
Capacity effect.Note, all capacity are all based on NiO/CNHs gross mass calculating in this task.Figure 24 is NiO/CNHs
Electrode is in 0.2Ag-1Current density under cycle performance curve, it can be seen that electrode has extraordinary cyclical stability, circulation
Capacity is still up to 1768mAh g after 100 circles-1, and coulombic efficiency is close to 100%, shows that Lithium-ion embeding/deintercalation has good
Good invertibity.Fig. 1 illustrates the excellent high rate performance of NiO/CNHs electrodes.It is respectively 0.2,0.5,1,2,3 in current density,
4,5 and 10Ag-1When, its average discharge capacity is respectively 1699,1380,1195,1020,823,687,599 and 453mAh g-1,
When electric current returns to 0.2A/g, its discharge capacity is recovered to 1485mAh/g rapidly, and gradually steady in subsequent charge and discharge cycles
It is fixed.As shown in figure 25, compared with other hollow NiO based structures, NiO/CNHs electrodes all have higher under different current densities
Capacity., it is apparent that porous carbon skeleton is NiO/CNHs tools in lithium ion/electrons spread schematic diagram (referring to Figure 26)
There are the major influence factors of outstanding high rate performance.First, porous characteristic is conducive to electrolyte infiltration and lithium ion diffusion.Its
Secondary, the high conductivity of carbon skeleton accelerates the transfer of electronics.Figure 27 is NiO/CNHs electrodes current density in lithium ion battery
For 5Ag-1When cycle performance curve.The capacity fluctuation of electrode is non-in the transition metal oxide electrode of lithium ion battery in figure
It is often universal.From Figure 27, in 5Ag-1When NiO/CNHs electrodes initial discharge capacity be 675mAh g-1, then in 250 circles
249mAh g are dropped to after circulation-1, slow afterwards to rise, when 1020 enclose, capacity has reached 424mAh g-1, finally, circulation
Capacity still remains 424mAh g after 1500 circles-1, it is the 62.8% of initial capacity.The capacity of beginning declines phenomenon and is attributable to
The formation of SEI films and irreversible transformation from part NiO to Ni.But the appearance of Ni nano particles improves the conduction of whole electrode
Property, improve charge-transfer dynamics.Therefore, hereafter capacity gradually rises in cyclic process.This is with being recycled to 250 circles and 500
The EIS test results carried out respectively during circle are consistent (referring to Figure 28).In Figure 28, show that Ni receives in the presence of two semicircles in high frequency region
The formation of rice grain cenotype.It is fitted by the equivalent circuit of Figure 28 illustrations, NiO/CNHs electrodes electrode/electro when 500 enclose
Solve liquid resistance (Rel=3.6 Ω) and charge transfer resistance (Rct=23 Ω) all than 250 circle when analog value (Rel=7.5 Ω, Rct=
57 Ω) it is small.Weinberg's impedance (the Z obtained in addition after fittingw) compare, the value (5.286 × 10 of 500 circles-3S·s1/2) than
The value (2.309 × 10 of 250 circles-3S·s1/2) greatly, it is fast before illustrating the diffusion ratio of this stage electrode.NiO/CNHs electrodes are such
Excellent cyclical stability is mainly influenceed by following factor：(1) in macro-scale, hollow-core construction can followed for whole electrode
Volume Changes during ring provide space；(2) on micro-scale, extra small NiO nano particles are dispersedly fixed on carbon shell,
The volumetric stress that each particle is produced in charge and discharge process effectively can be disperseed by carbon shell.
In a word, we design and are prepared for the NiO/CNHs composites of uniqueness.It combines hollow-core construction, amorphous nano
The advantage of porous carbon and extra small NiO nano particles.Compared with bowl shaped structure, CNHs inwall is fully utilized, and is between particle
NiO nano particles are contacted with CNHs can effectively reduce electrode resistance, and nanoporous carbon skeleton spreads there is provided more electrolyte
Path.Therefore, NiO/CNHs composite electrodes show excellent chemical property, and this is for it in high-performance lithium ion electricity
Possible application is very crucial in pond.
Claims (7)
1. a kind of preparation method of nickel oxide nanoparticle/carbon nanometer helmet composite (NiO/CNHs), comprises the following steps：
A, by improvedMethod synthesizes a diameter of 300~400nm SiO2Nanosphere：By 60~65ml isopropanol
It is mixed evenly with 20~24ml ultra-pure waters and 10~15ml ammoniacal liquor, adds 0.5~0.8ml tetraethyl orthosilicates, be stirred at room temperature
30~60min, then 4~6ml tetraethyl orthosilicates are added dropwise, product centrifugation is used water and alcohol washes by 30~40 DEG C of 2~3h of stirring again
3~5 times, 70~80 DEG C of 10~12h of vacuum drying；
B, by sol-gal process in SiO2Ball surface coating phenolic resin obtains RF/SiO2Nanosphere：Take 0.8~1g SiO2It is super
Sound is scattered in 65~70ml water and 25~30ml alcohol mixeding liquid, Jia 2 successively~2.4g cetyl trimethyl brominations
20~30min is stirred at room temperature in ammonium, 0.3~0.4g resorcinols, 0.1~0.2ml ammoniacal liquor, then Jia 0.3~0.5ml formalins,
30~40 DEG C of 7~8h of stirring, by product centrifugation again with water and alcohol washes 3~5 times, 70~80 DEG C of 10~12h of vacuum drying；
C, pass through hydro-thermal method prepare Ni (OH)2/RF/SiO2Nanosphere：By 0.8~1g RF/SiO2Nanosphere, 1.4~1.5g six
The mixture of nitric hydrate nickel, 1.3~1.5g hexamethylene tetramines and 10~15ml ethanol and 20~30ml ultra-pure waters is added
Into the stainless steel autoclave with polytetrafluoroethyllining lining, sealed reactor is put into 100~120 DEG C of electric dry ovens
10~12h is incubated, by product by being collected by centrifugation, 70~80 DEG C of 10~12h of vacuum drying；
D, by prepared Ni (OH)2/RF/SiO2Nanosphere in tube furnace Ar atmosphere under the conditions of 550~600 DEG C annealing 2~
3h, is cooled to after 320~350 DEG C again blowing air cooling, after cooling by product 60~70 in 2~3M sodium hydrate aqueous solution
DEG C 24~48h of immersion, product is centrifuged and clean with water 3~5 times, 70~80 DEG C are dried in vacuo 10~12h.
2. a kind of system of nickel oxide nanoparticle according to claim 1/carbon nanometer helmet composite (NiO/CNHs)
Preparation Method, it is characterised in that：In step a SiO is controlled by adjusting the ratio of isopropanol, ultra-pure water and ammoniacal liquor2The size of ball.
3. a kind of system of nickel oxide nanoparticle according to claim 1/carbon nanometer helmet composite (NiO/CNHs)
Preparation Method, it is characterised in that：Ni (OH) is prepared in step c2When, Ni (OH) is controlled by controlling hydrothermal temperature2Pattern.
4. a kind of system of nickel oxide nanoparticle according to claim 1/carbon nanometer helmet composite (NiO/CNHs)
Preparation Method, it is characterised in that：NiO pattern obtained by being controlled in step d as annealing temperature.
5. a kind of nickel oxide nanoparticle/carbon nanometer helmet composite (NiO/ according to any one of Claims 1-4
CNHs preparation method), including step in detail below：
A, pass through improveMethod methods synthesize a diameter of 300nm SiO2Nanosphere：By 63.3ml isopropanol with
23.5ml ultra-pure waters and 13ml ammoniacal liquor are mixed evenly, and add 0.6ml tetraethyl orthosilicates, 60min are stirred at room temperature, then be added dropwise
5ml tetraethyl orthosilicates, 35 DEG C of stirring 2h, by product centrifugation again with water and alcohol washes 3 times, 70 DEG C of vacuum drying 10h；
B, by sol-gal process in SiO2Ball surface coating phenolic resin obtains RF/SiO2Nanosphere：Take 1g SiO2Ultrasound point
Dissipate in 70ml water and 28ml alcohol mixeding liquid, 2.3g cetyl trimethylammonium bromides, 0.35g isophthalic two are added successively
30min is stirred at room temperature in phenol, 0.11ml ammoniacal liquor, then adds 0.5ml formalins, and product centrifugation is used water and wine by 35 DEG C of stirring 8h again
Seminal plasma is washed 3 times, 70 DEG C of vacuum drying 10h；
C, pass through hydro-thermal method prepare Ni (OH)2/RF/SiO2Nanosphere：By 1g RF/SiO2Nanosphere, the nitric hydrates of 1.45g six
Nickel, 1.4g hexamethylene tetramines, the mixture of 25ml ultra-pure water 10ml ethanol is added to polytetrafluoroethyllining lining not
In rust steel autoclave；Sealed reactor is put into 100 DEG C of electric dry ovens and is incubated 10h, by product by being collected by centrifugation, 70
DEG C vacuum drying 10h；
D, by prepared Ni (OH)2/RF/SiO2Nanosphere is warming up to 600 DEG C of conditions in tube furnace Ar atmosphere with 5 DEG C/min
Lower annealing 2h, is cooled to after 350 DEG C again blowing air cooling, 70 DEG C of immersions in 3M sodium hydrate aqueous solution by product after cooling
48h, product is centrifuged and cleaned with water 3 times, 70 DEG C of vacuum drying 10h.
6. the nickel oxide nanoparticle that preparation method according to claim 1 is obtained/carbon nanometer helmet composite (NiO/
CNHs), it carries out electro-chemical test as lithium ion battery electrode material, comprises the following steps：
It is prepared by a, working electrode：First by active material, acetylene black and binding agent Kynoar are according to 7:2:1 ratio is in N- first
It is coated on after being mixed evenly in base pyrrolidones on copper foil, then 10~12h of vacuum drying at 80~120 DEG C；
B, lithium ion battery assembling：Using active material NiO/CNHs as working electrode, lithium piece as to counter/reference electrode,
Barrier film is the films of Celgard 2500, and electrolyte is 1M LiPF6It is 1 to be dissolved in volume ratio:1:1 ethylene carbonate, carbonic acid two
In the mixed liquor of methyl esters and methyl ethyl carbonate, CR2016 type button cells, glove box are assembled into the glove box full of argon gas
Water oxygen value be respectively [O2]<1ppm,[H2O]<1ppm；
C, cyclic voltammetry are carried out with IVIUM electrochemical workstations, and it is 0.1~0.2mV/s, test voltage scope to sweep speed
For 0.01-3.0V；
D, electrochemical impedance test condition are that frequency range is 100kHz to 10mHz at room temperature；
E, constant current charge-discharge loop test are carried out using LAND CT2001A between voltage range 0.01-3.0V.
7. nickel oxide nanoparticle according to claim 6/carbon nanometer helmet composite (NiO/CNHs), it is used as lithium
Ion battery electrode materials carry out electro-chemical test, including step in detail below：
It is prepared by a, working electrode：First by active material (NiO/CNHs) 0.14g, acetylene black 0.4g and binding agent Kynoar
0.2g is coated on copper foil after being mixed evenly in 1-METHYLPYRROLIDONE, then is dried in vacuo 10h at 100 DEG C；
B, lithium ion battery assembling：Using active material NiO/CNHs as working electrode, lithium piece as to counter/reference electrode,
Barrier film is the films of Celgard 2500, and electrolyte is 1M LiPF6It is 1 to be dissolved in volume ratio:1:1 ethylene carbonate, carbonic acid two
In the mixed liquor of methyl esters and methyl ethyl carbonate, CR2016 type button cells, glove box are assembled into the glove box full of argon gas
Water oxygen value be respectively [O2]<1ppm,[H2O]<1ppm；
C, cyclic voltammetry are carried out with IVIUM electrochemical workstations, and it is 0.2mV/s to sweep speed, and test voltage scope is
0.01-3.0V；
D, electrochemical impedance test condition are that frequency range is 100kHz to 10mHz at room temperature；
E, constant current charge-discharge loop test are carried out using LAND CT2001A between voltage range 0.01-3.0V.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107715877A (en) * | 2017-10-16 | 2018-02-23 | 太原理工大学 | A kind of hollow mesoporous carbosphere shell confinement copper catalyst and preparation method and application |
| CN109841810A (en) * | 2019-01-07 | 2019-06-04 | 浙江工业大学 | A kind of preparation method and application of Ni-NiO/C composite material |
| CN110444745A (en) * | 2019-07-22 | 2019-11-12 | 华中科技大学 | A kind of porous hollow carbon material of carried metal phosphide, its preparation and application |
| CN112201782A (en) * | 2020-10-16 | 2021-01-08 | 西南大学 | Nickel phosphide/carbon/nickel phosphide composite material and preparation method and application thereof |
| CN112563500A (en) * | 2020-12-04 | 2021-03-26 | 广东工业大学 | Preparation method of hollow bowl-shaped carbon-based metal/selenium/oxygen co-doped composite material and lithium ion battery |
| CN113611945A (en) * | 2021-07-30 | 2021-11-05 | 柴同明 | Mobile rechargeable battery of new energy automobile |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569768A (en) * | 2011-08-19 | 2012-07-11 | 吴杭春 | High-specific-area carbon/metallic oxide composite electrode material of lithium battery, electrode and preparation methods for high-specific-area carbon/metallic oxide composite electrode material and electrode |
| CN103346299A (en) * | 2013-06-08 | 2013-10-09 | 上海大学 | In-situ etching method for preparing hollow tin-based oxide/carbon composite nano-material |
| CN104900421A (en) * | 2015-04-21 | 2015-09-09 | 扬州大学 | Preparation method of nickel oxide/carbon sphere composite material |
-
2017
- 2017-06-30 CN CN201710521079.6A patent/CN107204450B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569768A (en) * | 2011-08-19 | 2012-07-11 | 吴杭春 | High-specific-area carbon/metallic oxide composite electrode material of lithium battery, electrode and preparation methods for high-specific-area carbon/metallic oxide composite electrode material and electrode |
| CN103346299A (en) * | 2013-06-08 | 2013-10-09 | 上海大学 | In-situ etching method for preparing hollow tin-based oxide/carbon composite nano-material |
| CN104900421A (en) * | 2015-04-21 | 2015-09-09 | 扬州大学 | Preparation method of nickel oxide/carbon sphere composite material |
Non-Patent Citations (2)
| Title |
|---|
| JUYOUNG YUN，ET AL.: ""Fabrication of monodisperse nitrogen-doped carbon double-shell hollow nanoparticles for supercapacitors"", 《RSC ADV.》 * |
| LEI LI，ET AL.: ""MnO2 Nanosheets Grown on Nitrogen-Doped Hollow Carbon Shells as a High-Performance Electrode for Asymmetric Supercapacitors"", 《CHEM. EUR. J.》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107715877A (en) * | 2017-10-16 | 2018-02-23 | 太原理工大学 | A kind of hollow mesoporous carbosphere shell confinement copper catalyst and preparation method and application |
| CN107715877B (en) * | 2017-10-16 | 2021-02-19 | 山西潞安矿业(集团)有限责任公司 | Hollow mesoporous carbon microsphere shell confinement copper catalyst and preparation method and application thereof |
| CN109841810A (en) * | 2019-01-07 | 2019-06-04 | 浙江工业大学 | A kind of preparation method and application of Ni-NiO/C composite material |
| CN110444745A (en) * | 2019-07-22 | 2019-11-12 | 华中科技大学 | A kind of porous hollow carbon material of carried metal phosphide, its preparation and application |
| CN110444745B (en) * | 2019-07-22 | 2021-10-15 | 华中科技大学 | Porous hollow carbon material loaded with metal phosphide, and preparation and application thereof |
| CN112201782A (en) * | 2020-10-16 | 2021-01-08 | 西南大学 | Nickel phosphide/carbon/nickel phosphide composite material and preparation method and application thereof |
| CN112563500A (en) * | 2020-12-04 | 2021-03-26 | 广东工业大学 | Preparation method of hollow bowl-shaped carbon-based metal/selenium/oxygen co-doped composite material and lithium ion battery |
| CN113611945A (en) * | 2021-07-30 | 2021-11-05 | 柴同明 | Mobile rechargeable battery of new energy automobile |
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