CN105845889A - NiCo<2>O<4> composite material and preparation method therefor, and application of composite material in lithium ion battery - Google Patents
NiCo<2>O<4> composite material and preparation method therefor, and application of composite material in lithium ion battery Download PDFInfo
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- CN105845889A CN105845889A CN201610239753.7A CN201610239753A CN105845889A CN 105845889 A CN105845889 A CN 105845889A CN 201610239753 A CN201610239753 A CN 201610239753A CN 105845889 A CN105845889 A CN 105845889A
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/36—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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- 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
- H01M4/58—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
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- 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 invention relates to an NiCo<2>O<4> composite material and a preparation method therefor, and an application of the composite material in a lithium ion battery, and belongs to the development technical field of the high-capacity high-energy-density lithium ion battery. According to the preparation method, an Ni-Co dual-layer metal hydroxide is synthesized through a simple liquid phase method; then the metal hydroxide is further calcined to obtain a multiple-stage nanostructure; and next, enabling the multiple-stage nanostructure to be well adsorbed on graphene through an extremely-thin dual-metal nano slice via electrostatic adsorption. The invention also provides the high-performance lithium ion battery adopting the negative electrode material. The composite material is reasonable in material structure and component design, and simple in preparation process; the obtained product is excellent in performance, so that large-scale industrial application can be realized conveniently; and when the obtained composite material is applied to the lithium ion battery, the lithium ion battery has the advantages of high lithium storage specific capacity, stable electrical performance, and the like.
Description
Technical field
The present invention relates to a kind of NiCo2O4Composite and preparation method thereof and its application on lithium ion battery；Belong to Gao Rong
Amount, lithium ion battery with high energy density development technique field.
Background technology
Lithium ion battery is used for portable electric appts and the master of electric automobile/cell mixed power automobile (EV/HEV) as one
Energy storage vehicles is wanted to be extensively studied in the past few decades due to its high-energy-density, long-life and environment friendly.
At present, topmost research direction finds the electrode material with high-energy-density and cyclical stability to carry out substitute goods
Graphite (energy density only 372mAh g-1)。
Transition metal oxide (especially Co3O4) it is higher than the high theoretical capacity (890mAh of twice relative to graphite due to it
g-1) receive much concern being applied on lithium ion battery, it is expected to meet the high request of future source of energy system.Bimetallic oxide
Such as: ZnCo2O4、CuFe2O4And ZnSnO3Etc. having variable oxidation state, high electrical conductance, it is most important that cost
Low, environmental protection and aboundresources, being recently in the news is a kind of preferable potential electrode material.In numerous bimetallic oxides,
NiCo2O4It is a kind of electrode material most with prospects, because it has high electrochemistry electrical conductance, the expansion of low ion-electron
Dissipate resistance and readily permeable electrolyte.NiCo2O4With Co3O4Isomorphism, owing to Ni with Co atomic radius is more or less the same, therefore
Ni replaces its structure of position of a Co and will not change；And the addition of Ni not only reduces the cost of material and carries significantly
High electrical conductivity, from 3.1*10-5S cm-1Increase to 0.1-0.3S cm-1, therefore further enhance high current charge-discharge
Ability.But, with Co3O4The material disintegrating occurred during embedding lithium with de-lithium causes significantly irreversible capacity loss
Cyclical stability is poor, becomes NiCo2O4Topmost defect.A kind of method of effective modification is synthesis NiCo2O4With carbon
Composite, this can not only stop active material peeling from current substrate, additionally it is possible to improve NiCo2O4Electrical conductance.
Graphene, a kind of new Two-dimensional Carbon material, there is the biggest specific surface area, fabulous electrical conductance, structural variability and chemistry
Stability, is found to start the most widely by chemist and the concern of material scholar and research from it.Therefore, NiCo2O4In
Add Graphene to construct a conductive network and effectively stop the Volume Changes occurred in chemical reaction.Forefathers have also been made one
A little relevant researchs, such as: the NiCo of lou et al. report2O4Raw on graphene oxide: Gao GX, Wu HB, Lou XW
(2014)Citrate-Assisted Growth of NiCo2O4Nanosheets on Reduced Graphene Oxide for Highly
Reversible Lithium Storage.Adv Energy Mater 4:1002-1008；By with citric acid as adjuvant by nitric acid
Nickel, cobalt nitrate and Graphene wash the method for drying and calcining after reacting while stirring so that nickel cobalt oxide length is on Graphene
Form nanometer sheet；The electrode material that the method obtains is respectively 200 and 500mA g in current density-150 reversible appearances of lower circulation
Amount is maintained at 954.3 and 656.5mAh g-1, and it is respectively 87.1% and 74.6% relative to the second circle capability retention；But greatly
Capacity boost under electric current is the most inconspicuous.The NiCo of lu et al. report2O4/ graphene complex array performance on lithium ion battery
Improve, Chen YJ, Zhu J, Qu BH, Lu BG, Xu Z (2014) Graphene improving lithium-ion battery
performance by construction of NiCo2O4/graphene hybrid nanosheet arrays.Nano Energy 3:88-94；
After the graphene oxide stirring 2h of the nickel nitrate after dissolving and cobalt nitrate and ultrasonic 1h, add ammonium fluoride and urea stirring
Add 120 DEG C of hydro-thermals 2h of nickel screen that HCl treatment is crossed after dissolving, be vacuum dried again after washing for several times, the side of calcining under last argon gas
Method obtains cobalt acid nickel and Graphene length combination electrode material on nickel screen.This material is respectively 100,200,300 in current density
mA g-110 capacity of lower circulation keep being respectively 1267,1034,806mAh g-1, its capacity is improved and relatively stable,
And electrical conductivity also gets a promotion；But its preparation technology requires higher and complicated, and the high rate during charging-discharging of material is not carried
High.
Summary of the invention
It is an object of the invention to for NiCo2O4Lithium ion deintercalation mechanism, easily occur that when discharge and recharge volumetric expansion causes
The shortcoming of material disintegrating, buffers change NiCo by being combined with Graphene2O4The stress produced when lithium ion enters, inherently
Improve NiCo2O4Removal lithium embedded cyclical stability, it is provided that a kind of a kind of NiCo2O4Self-assembled nanometer floral material multistage with Graphene
And prepare and application.
One NiCo2O4 composite of the present invention, described NiCo2O4 composite is that NiCo2O4 passes through multistage with Graphene
The nano flower material of self assembly；Described nano flower material is obtained by Electrostatic Absorption by stratiform NiCo2O4 and lamellar graphite alkene
Arrive；Layered Graphene accounts for the 5-8% of described nano flower material gross mass.
The preparation method of the present invention a kind of NiCo2O4 composite；Comprise the steps: cobalt chloride, nickel chloride and six first
Urotropine is dissolved in containing in the spirituous aqueous solution, heats, is added thereto to Graphene and/or graphite oxide after obtaining green solution
Alkene, washs after mixing, is dried, calcines, obtain NiCo2O4Self-assembled nanometer floral material multistage with Graphene.
One NiCo of the present invention2O4The preparation method of composite；In molar ratio, the ratio of Co:Ni=2:1 join take cobalt chloride and
Nickel chloride.
One NiCo of the present invention2O4The preparation method of composite；In molar ratio, hexamethylenetetramine: Co=10-12:1 joins
Take hexamethylenetetramine.
One NiCo of the present invention2O4The preparation method of composite；Containing in the spirituous aqueous solution；Alcohol and the molar ratio of water
For 0-1:9, it is preferably 1:9.
One NiCo of the present invention2O4The preparation method of composite；2000-2500ml is added containing spirituous water by 1g cobalt chloride
Cobalt chloride, nickel chloride and hexamethylenetetramine are dissolved in containing in the spirituous aqueous solution by the ratio of solution, and stirring is to mixing.
One NiCo of the present invention2O4The preparation method of composite；The temperature of heating is 90-130 DEG C, be preferably 100-120 DEG C,
More preferably 120 DEG C.
One NiCo of the present invention2O4The preparation method of composite；After obtaining green solution, generate NiCo by theory2O4Quality
10-15% be added thereto to Graphene and/or graphene oxide.Described Graphene is few layer graphene；The layer of described Graphene
The mixture that number less than or equal to 5 layers, is preferably made up of the Graphene of the different numbers of plies.
One NiCo of the present invention2O4The preparation method of composite；Gained obtains before green solution is nickel cobalt double-metal hydroxide
Drive body.
One NiCo of the present invention2O4The preparation method of composite；Graphene is added, after Graphene is added completely in ultrasonic state
Continue ultrasonic mixing 10～15min.Described ultrasonic frequency is 20K-40KHz.
One NiCo of the present invention2O4The preparation method of composite；Washing is to carry out suction filtration with distilled water for washing lotion；Until washing out
When the concentration of chlorion is less than or equal to 0.01mol/L in liquid, terminate washing.
One NiCo of the present invention2O4The preparation method of composite；Described be dried into vacuum drying, described vacuum drying time, control
Stove internal gas pressure processed is 5-15h less than or equal to 0.1Pa, control drying time.
One NiCo of the present invention2O4The preparation method of composite；The temperature of described calcining is 200-350 DEG C, is preferably 250-300
DEG C, more preferably 260 DEG C, calcining time be 1-3h, be preferably 1.5-2.5h, more preferably 2h.
One NiCo of the present invention2O4The preparation method of composite；When room temperature to calcining heat, controlling heating rate is
1-3 DEG C/min, preferably 2-2.5 DEG C/min, more preferably 2 DEG C/min.
One NiCo of the present invention2O4The application of composite, including as lithium ion battery negative material.
One NiCo of the present invention2O4The application of self-assembled nanometer floral material multistage with Graphene, is 1-2 micron by granularity
NiCo2O4Self-assembled nanometer flower multistage with Graphene, as active cathode material, is prepared as lithium ion battery.
One NiCo of the present invention2O4The application of self-assembled nanometer floral material multistage with Graphene, is 1-2 micron by granularity
NiCo2O4Self-assembled nanometer flower multistage with Graphene is as active cathode material, using metal lithium sheet as anode, with the LiF of 1M6
It is dissolved in the EC/DMC that volume ratio is 1:1 as electrolyte, makes lithium ion battery using polypropylene screen as barrier film；Described lithium
After ion battery circulates 35 times, reversible lithium storage specific capacity is up to 1206.9mAh g-1.It is up to 5000mA g in current density-1Time
NiCo2O4/ graphene composite material shows 150mAh g-1Stabilization ratio capacity, and return to 50mA g when current density-1Time
Its specific discharge capacity may return to and stablize at 1470mAh g-1。
Principle and advantage
The present invention compared with prior art, has the advantage that
(1) phase method of modifying the most than ever is by NiCo2O4For nanometer, or carbon cladding, this research is by simple liquid
Phase method synthesis Ni-Co layered double hydroxide, one-step calcination of going forward side by side obtains multistage nanostructured by very thin
Bimetal nano thin slice be perfectly adhered on Graphene by the effect of Electrostatic Absorption, this novelty is many
Level nanometer flower structure can stop the self aggregation of two-dimension nano materials effectively；Graphene is possible not only to make simultaneously
NiCo is strengthened for conductive network2O4The electric conductivity of nanometer sheet, it is also possible to the stress that buffering lithium ion deintercalation produces.
(2), for comparing negative material graphite theoretical specific capacity 372mAh/g of current commercialization, the present invention provides
NiCo2O4/ graphene composite material has the most superior performance, such as, reversible lithium storage after circulating 35 times
Specific capacity is up to 1206.9mAh g-1, and pure NiCo2O4From initial 1071.1mAh g-1Circulate 30 times
After be rapidly decreased to only 218.2mAh g-1；Additionally, be up to 5000mA g in current density-1Time NiCo2O4/
Graphene composite material shows 150mAh g-1Stabilization ratio capacity, and return to 50mA when current density
g-1Time its specific discharge capacity may return to and stablize at 1470mAh g-1。
Accompanying drawing explanation
Fig. 1 (a) is NiCo in embodiment 12O4/ graphene composite material (curve back end is stronger) and pure NiCo2O4(curve
Relative smooth) XRD spectrum；Fig. 1 (b) is gained NiCo in embodiment 12O4The differential thermal figure of/graphene composite material.
Fig. 2 (a) is pure NiCo in embodiment 12O4TEM figure；
Fig. 2 (b) is pure NiCo in embodiment 12O4TEM figure；
Fig. 2 (c) is pure NiCo in embodiment 12O4HTEM figure；
Fig. 2 (d) is NiCo in embodiment 12O4The TEM figure of/graphene composite material；
Fig. 2 (e) is NiCo in embodiment 12O4The TEM figure of/graphene composite material；
Fig. 2 (f) is NiCo in embodiment 12O4The HTEM figure of/graphene composite material.
Fig. 3 is NiCo in embodiment 12O4SEM figure.
Fig. 4 (a) is the NiCo of embodiment 12O4SEM figure before the circulation of/graphene composite material；
Fig. 4 (b) is the NiCo of embodiment 12O4/ graphene composite material circulates the SEM figure after 50 times.
Fig. 5 (a) is NiCo in embodiment 22O4The charge and discharge process voltage of/graphene composite material and specific capacity curve；
Fig. 5 (b) is NiCo2O4Charge and discharge process voltage and specific capacity curve；
Fig. 5 (c) is NiCo in embodiment 22O4/ graphene composite material charge and discharge cycles stability curve；
Fig. 5 (b) is NiCo2O4Charge and discharge cycles stability curve；
Fig. 5 (e) is NiCo in embodiment 22O4/ graphene composite material CV curve map
Fig. 5 (f) is NiCo2O4CV curve map.
Fig. 6 (a) is NiCo in embodiment 22O4The curve of double curvature figure of/graphene composite material；
Fig. 6 (b) is NiCo in embodiment 22O4The AC impedance curve of/graphene composite material.
Can be seen that from Fig. 1 (a) and pure NiCo2O4Compare NiCo2O4The diffracting spectrum of/graphene composite material at 2 θ is
There is an obvious amorphous diffraction maximum at 20～30 °, which demonstrate the existence of Graphene；Temperature is can be seen that from Fig. 1 (b)
About 300-450 ° of sharp-pointed exothermic peak represents Graphene and there occurs that decomposition reaction result in the mass loss i.e. graphite of 6.88%
The content of alkene.
Pure NiCo is can be seen that from Fig. 2 (a)2O4For very thin two-dimensional layer；Pure NiCo is can be seen that from Fig. 2 (b)2O4
The relatively big nearly micron order of area；From Fig. 2 (c), can be seen that high-resolution is mutually for typical NiCo2O4Striped picture；From Fig. 2 (d)
In can be seen that NiCo2O4/ graphene composite material is nano flower pattern；NiCo is can be seen that from Fig. 2 (e)2O4With graphite
Alkene combines very well；From Fig. 2 (f), can be seen that, under high-resolution, there is NiCo2O4Typical striped picture and the non-crystal bar of Graphene
Line picture and the two combination are very well.
As can be seen from Figure 3 NiCo2O4For two-dimensional sheet.
The NiCo before circulation is can be seen that from Fig. 4 (a)2O4/ graphene composite material is nano flower-like；Can from Fig. 4 (b)
To find out the NiCo after circulating 50 circles2O4/ graphene composite material still presents nano flower pattern, in conjunction with Fig. 4 (a), Fig. 4 (b)
In can be seen that Graphene there was added help stop NiCo2O4Volume in cyclic process is pulverized, and largely maintains
Its pattern.
In Fig. 5 (a), No. 1 curve represents NiCo2O4The capacity voltage of the 1st discharge and recharge of/graphene composite material, No. 2 curves
Represent NiCo2O4The capacity voltage of the 2nd discharge and recharge of/graphene composite material, No. 10 curves represent NiCo2O4/ Graphene is combined
The capacity voltage of the 10th discharge and recharge of material, No. 30 curves represent NiCo2O4The 30th discharge and recharge of/graphene composite material
Capacity voltage；NiCo is can be seen that from Fig. 5 (a)2O4/ graphene composite material charging/discharging voltage platform after the 2nd time is obvious
And stable, reversible capacity is higher than 1200mAh g-1。
In Fig. 5 (b), No. 1 curve represents NiCo2O4The capacity voltage of the 1st discharge and recharge of material, No. 10 curves represent NiCo2O4
The capacity voltage of the 10th discharge and recharge of material, No. 30 curves represent NiCo2O4The capacity voltage of the 30th discharge and recharge of material；From
Fig. 5 (b) can be seen that pure NiCo2O4Material capacity is less than 220mAh g after constantly declining 30 circles-1；In conjunction with Fig. 5 (a),
Fig. 5 (b) can be seen that NiCo2O4/ graphene composite material constant current charge-discharge performance is far above pure NiCo2O4Material.
NiCo is can be seen that from Fig. 5 (c)2O4After/graphene composite material circulation 35 circle, reversible capacity is maintained at 1206.9mAh
g-1；Pure NiCo is can be seen that from Fig. 5 (d)2O4After material circulation 35 times, reversible capacity is rapidly decreased to 218.2mAh g-1。
In Fig. 5 (e), No. 1 curve represents NiCo2O4The CV curve of/graphene composite material first charge-discharge, No. 2 curve tables
Show NiCo2O4The CV curve of the 2nd discharge and recharge of/graphene composite material, No. 3 curves represent NiCo2O4/ Graphene composite wood
Expect that the CV curve of the 3rd discharge and recharge, No. 4 curves represent NiCo2O4The CV curve of/graphene composite material the 4th discharge and recharge；
NiCo is can be seen that from Fig. 5 (e)2O4Except there is amorphous Li first in/graphene composite material2O and solid electrolyte film
Outside reaction of formation, reaction registration afterwards is the highest.
In Fig. 5 (f), No. 1 curve represents pure NiCo2O4The CV curve of material first charge-discharge, No. 2 curves represent pure NiCo2O4
The CV curve of the 2nd discharge and recharge of material, No. 3 curves represent pure NiCo2O4The CV curve of the 3rd discharge and recharge of material, No. 4
Curve represents pure NiCo2O4The CV curve of material the 4th discharge and recharge；Pure NiCo is can be seen that from Fig. 5 (f)2O4Material
Discharge and recharge reaction is more and more weak；NiCo is can be seen that in conjunction with Fig. 5 (e), Fig. 5 (f)2O4/ graphene composite material stable circulation
Property far above pure NiCo2O4Material.
NiCo is can be seen that from Fig. 6 (a)2O4/ Graphene electrodes is at 100mA g-1Under electric current, circulation maintains 1,207 10 times
mAh g-1Reversible capacity, 500mA g-1Circulating 10 reversible capacities under electric current is 1038.1mAh g-1, 1000mA g-1
Circulating 10 reversible capacities under electric current is 666.3mAh g-1, 2000mA g-1Circulating 10 reversible capacities under electric current is 319.5
mAh g-1, and 5000mA g-1Circulate 10 reversible capacities under electric current to remain to maintain 150mAh g-1；When returning once again to
50mA g-1Current density time, its reversible capacity can recover and stable at 1470mAh g-1；Can from Fig. 6 (b)
Go out NiCo2O4Semicircle diameter much larger than NiCo2O4The semicircle diameter i.e. NiCo of/Graphene2O4Charge-transfer resistance more
High.
Detailed description of the invention
It is intended to further illustrate the present invention below in conjunction with embodiment, and the unrestricted present invention.
Embodiment 1
Weigh the cobalt chloride hexahydrate (CoCl of 0.2379g commercialization2·6H2O), six hydration chlorine of 0.1188g commercialization
Change nickel (NiCl2·6H2O), the hexamethylenetetramine (C of 1.6822g commercialization6H12N4), they are dissolved in 200ml
Prepare in advance according to the deionized water that volume ratio is 9:1 and absolute ethyl alcohol (C2H6O2) mixed liquor in；By institute
Obtain solution to transfer to, in the three neck round bottom flask that capacity is 500ml, round-bottomed flask be put into the digital display equipped with methyl-silicone oil
Being stirred reaction in heat collecting type agitator, arranging temperature is 120 DEG C, and the reaction time is to cool down with stove after 30min
I.e. available green Co (OH)2With Ni (OH)2Mixture solution (Ni-Co LDH).By the percent mass of 10%
Number adds graphene oxide solution (electronegative) in the Co (OH) obtained2With Ni (OH)2Mixed solution (positively charged)
In, and put into ultrasonic 2 times (frequency is 40KHz) in Ultrasound Instrument, each 10-15min, with ensure graphene oxide with
Ni-Co LDH electrostatic self-assembled is combined the most layer by layer；After deionized water and alcohol filtering and washing 4-5 time, will obtain
Filter cake be put in vacuum drying chamber be dried；The dried solid obtained is put into 260 DEG C of calcining 2h in Muffle furnace,
Programming rate is 2 DEG C/min, cools to room temperature with the furnace and i.e. can get NiCo2O4Self-assembled nanometer multistage with Graphene flower material
Material.
Embodiment 2
NiCo2O4With Graphene active material and acetylene black (conductive agent), PVDF (binding agent) 7:1.5:1.5 in mass ratio
Ratio mixing, grind until the PVDF of white mixes in the material the most uniformly, add be about PVDF 1/0.2379 matter
The NMP of amount as solvent and stirs；After continuously stirred about 24 hours, the active material slurry stirred is evenly coated with
On Cu paper tinsel, it is put in air after it dries naturally, moves on to 90 DEG C dry 12 hours in vacuum drying chamber；Take out dried
Electrode slice and by circular electric pole piece that its punching is diameter about 10mm；In vacuum glove box, carry out assembling obtain for electrically
The button cell (with lithium sheet as negative pole) that can test, tests its electrical property after placing about 6h liquid to be electrolysed complete wetting after compression.
Li/NiCo2O4Being assembled in the glove box (Mbraum, Germany) being filled with high-purity argon gas of button cell (2016 model)
Carry out.Using metal lithium sheet as to electrode, using polypropylene screen as barrier film, 1M LiPF6It is dissolved in ethyl carbonate/dimethyl carbonate
(EC/DMC) (1:1, volume ratio) is as electrolyte, and the material of synthesis is as the negative material of battery.Filling of lithium ion battery
Electricity and discharge performance test are carried out at room temperature in blue electrical testing system, and the voltage range of test is 0-3V reference and Li/Li+。
Cyclic voltammetry is carried out in IM6ex electrochemical workstation system, and test rate is 0.1mV s-1。
Fig. 5 is the NiCo in embodiment 22O4/ graphene composite material (1,2,10 and 30 circle) (a) and NiCo2O4(1、
10 and 30 circles) the charge and discharge process voltage of (b) and specific capacity curve；Charge and discharge cycles stability curve (c), (d)；1st
To CV curve (e) of the 4th circulation, (f).
Fig. 6 is (a) NiCo in embodiment 22O4/ graphene composite material multiplying power (current density unit mA g-1) and (b) friendship
Flow impedance curve (NiCo2O4/ graphene composite material half circular diameter is less, pure NiCo2O4Material half circular diameter is significantly larger).
Claims (10)
1. a NiCo2O4Composite, it is characterised in that: described NiCo2O4Composite is NiCo2O4Lead to Graphene
Cross the nano flower material of multistage self assembly；Described nano flower material is inhaled by electrostatic with lamellar graphite alkene by stratiform NiCo2O4
Attached and obtain；Layered Graphene accounts for the 5-8% of described nano flower material gross mass.
2. prepare NiCo as claimed in claim 1 for one kind2O4The method of composite；It is characterized in that: comprise the steps:
Cobalt chloride, nickel chloride and hexamethylenetetramine are dissolved in containing in the spirituous aqueous solution, heating, obtain after green solution to it
Middle addition Graphene and/or graphene oxide, wash after mixing, be dried, calcine, obtain NiCo2O4Multistage with Graphene
Self-assembled nanometer floral material.
A kind of NiCo the most according to claim 22O4The preparation method of composite；It is characterized in that:
In molar ratio, the ratio of Co:Ni=2:1 is joined and is taken cobalt chloride and nickel chloride；
In molar ratio, hexamethylenetetramine: Co=10-12:1, joins and takes hexamethylenetetramine；
Described containing in the spirituous aqueous solution；Alcohol is 0-1:9 with the molar ratio of water.
A kind of NiCo the most according to claim 32O4The preparation method of composite；It is characterized in that:
The 2000-2500ml ratio containing the spirituous aqueous solution is added by cobalt chloride, nickel chloride and six methines four in 1g cobalt chloride
Amine solvent is in containing in the spirituous aqueous solution, and stirring is to mixing.
A kind of NiCo the most according to claim 22O4The preparation method of composite；It is characterized in that: the temperature of heating
For 90-120 DEG C.
A kind of NiCo the most according to claim 22O4The preparation method of composite；It is characterized in that: obtain green molten
After liquid, generate NiCo by theory2O4The 10-15% of quality is added thereto to Graphene and/or graphene oxide.Described Graphene
For few layer graphene；The number of plies of described Graphene is less than or equal to 5 layers.
A kind of NiCo the most according to claim 22O4The preparation method of composite；It is characterized in that: in ultrasonic state
Adding Graphene, Graphene continues ultrasonic mixing 10～15min after being added completely into；Described ultrasonic frequency is 20K-40KHz.
A kind of NiCo the most according to claim 22O4The preparation method of composite；It is characterized in that:
Washing is to carry out suction filtration with distilled water for washing lotion；During until the concentration of chlorion is less than or equal to 0.01mol/L in eluate,
Terminate washing；
Described it is dried as vacuum drying, during described vacuum drying, controls stove internal gas pressure less than or equal to 0,1Pa, control drying time and be
5-15h。
The temperature of described calcining is 200-350 DEG C, the time of calcining is 1.5-2.5h；When room temperature to calcining heat, control
Heating rate is 1-3 DEG C/min.
9. according to a kind of NiCo that claim 2-7 is arbitrarily described2O4The preparation method of composite；It is characterized in that: its institute
The NiCo of preparation2O4The application of self-assembled nanometer floral material multistage with Graphene includes as lithium ion battery negative material.
A kind of NiCo the most according to claim 12O4The application of composite, it is characterised in that: it is that 1-2 is micro-by granularity
The NiCo of rice2O4Self-assembled nanometer flower multistage with Graphene is as active cathode material, using metal lithium sheet as anode, with 1M
LiF6It is dissolved in the EC/DMC that volume ratio is 1:1 as electrolyte, using polypropylene screen as barrier film, makes lithium ion battery；
After described lithium ion battery circulates 35 times, reversible lithium storage specific capacity is up to 1206.9mAh g-1.It is up to 5000mA in current density
g-1Time NiCo2O4/ graphene composite material shows 150mAh g-1Stabilization ratio capacity, and return to 50mA g when current density-1
Time its specific discharge capacity may return to and stablize at 1470mAh g-1。
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