CN105845889B - A kind of NiCo2O4Composite material and preparation method and its application on lithium ion battery - Google Patents
A kind of NiCo2O4Composite material and preparation method and its application on lithium ion battery Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The present invention relates to a kind of NiCo2O4Composite material and preparation method and its application on lithium ion battery；Belong to high capacity, lithium ion battery with high energy density development technique field.The present invention synthesizes Ni-Co layered double hydroxide using simple liquid phase method, and one-step calcination of going forward side by side obtains multistage nanostructure and is perfectly adhered on graphene by very thin bimetal nano thin slice by the effect of Electrostatic Absorption.The present invention also provides the high performance lithium ion batteries for using the negative electrode material.Material structure of the present invention, composition design is reasonable, preparation process is simple, products obtained therefrom function admirable is convenient for large-scale industrial application.Its products obtained therefrom has the advantages such as storage lithium specific capacity height, stable electrical properties when being used as lithium ion battery.
Description
Technical field
The present invention relates to a kind of NiCo2O4Composite material and preparation method and its application on lithium ion battery；Belong to
High capacity, lithium ion battery with high energy density development technique field.
Background technique
Lithium ion battery is used for portable electronic device and electric car/cell mixed power automobile (EV/HEV) as a kind of
Main energetic storage medium it is extensive in the past few decades due to its high-energy density, long-life and environment friendly
Ground research.Currently, most important research direction is exactly to find the electrode material with high-energy density and cyclical stability to replace
Graphite (the energy density only 372mAh g of generation commercialization-1)。
Transition metal oxide (especially Co3O4) the high theoretical capacity (890mAh that is higher than relative to graphite twice due to it
g-1) be concerned on being applied to lithium ion battery, it is expected to meet the high request of future source of energy system.Bimetallic oxide
Such as: ZnCo2O4、CuFe2O4And ZnSnO3Deng with variable oxidation state, high electrical conductance, it is most important that at low cost, ring
It protects and resourceful, being reported recently is a kind of ideal potential electrode material.In numerous bimetallic oxides,
NiCo2O4It is a kind of electrode material most with prospects, because there is high electrochemistry electrical conductance, low ion-electron to expand for it
Dissipate resistance and readily permeable electrolyte.NiCo2O4With Co3O4Isomorphism, since Ni and Co atomic radius is not much different, Ni is taken
Generation its structure of position of one Co will not change；And the addition of Ni not only reduces the cost of material and significantly improves
Conductivity, from 3.1*10-5S cm-1Increase to 0.1-0.3S cm-1, therefore further enhance the energy of high current charge-discharge
Power.However, and Co3O4The material disintegrating occurred during embedding lithium and de- lithium leads to significantly irreversible capacity loss circulation
Stability is poor, becomes NiCo2O4Most important defect.A kind of effectively modified method is synthesis NiCo2O4It is compound with carbon
Material, this can not only prevent active material from the peeling on current substrate, additionally it is possible to improve NiCo2O4Electrical conductance.Graphite
A kind of alkene, new two-dimentional carbon material, has very big specific surface area, fabulous electrical conductance, structural variability and chemical stabilization
Property, the just widely concern and research by chemist and material scholar since being found it.Therefore, NiCo2O4Middle addition stone
Black alkene can construct a conductive network and effectively prevent the volume change occurred in chemical reaction.Some phases have also been made in forefathers
The research of pass, such as: the NiCo of lou et al. report2O4Life is 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 lemon
Acid washs drying and calcining method after reacting nickel nitrate, cobalt nitrate and graphene while stirring as adjuvant, so that nickel
Cobalt/cobalt oxide is grown forms nanometer sheet on graphene；The electrode material that this method obtains is respectively 200 and 500mA in current density
g-150 reversible capacities of lower circulation are maintained at 954.3 and 656.5mAh g-1, and enclose capacity retention ratio relative to second and be respectively
87.1% and 74.6%；But the capacity boost under high current is not obvious.The NiCo of lu et al. report2O4/ graphene complex
Array performance on lithium ion battery improves, 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；By by dissolved nickel nitrate and cobalt nitrate and super
After the graphene oxide stirring 2h of sound 1h, 120 DEG C of nickel screen that HCl treatment is crossed are added after ammonium fluoride and urea stirring and dissolving is added
Hydro-thermal 2h is dried in vacuo again after washing for several times, and the method calcined under last argon gas obtains cobalt acid nickel and graphene is grown on nickel screen
Combination electrode material.The material is respectively 100,200,300 mA g in current density-1Lower 10 capacity of circulation keep difference
For 1267,1034,806mAh g-1, capacity is improved and relatively stable, and conductivity also gets a promotion；But it prepares work
Skill is more demanding and complicated, and the high rate during charging-discharging of material is not improved.
Summary of the invention
The purpose of the present invention is be directed to NiCo2O4Lithium ion deintercalation mechanism, be easy to appear volume expansion in charge and discharge
The shortcomings that leading to material disintegrating, by with graphene it is compound come buffer become NiCo2O4The stress generated when lithium ion enters, from this
Improve NiCo in matter2O4Removal lithium embedded cyclical stability, a kind of NiCo is provided2O4With graphene multistage self-assembled nanometer flower
Material and its preparation and application.
A kind of NiCo2O4 composite material of the present invention, it is more that the NiCo2O4 composite material is that NiCo2O4 and graphene pass through
Nanometer floral material made of grade self assembly；The nanometer floral material passes through Electrostatic Absorption by stratiform NiCo2O4 and lamellar graphite alkene
And it obtains；Layered graphene accounts for the 5-8% of the nanometer floral material gross mass.
A kind of preparation method of NiCo2O4 composite material of the present invention；Include the following steps: cobalt chloride, nickel chloride and six
Methine tetramine is dissolved in containing in spirituous aqueous solution, and graphene and/or oxygen is added after obtaining green solution in heating thereto
Graphite alkene washs after mixing, is dry, calcining, obtaining NiCo2O4With graphene multistage self-assembled nanometer floral material.
A kind of NiCo of the present invention2O4The preparation method of composite material；In molar ratio, the ratio of Co:Ni=2:1, which is matched, takes chlorination
Cobalt and nickel chloride.
A kind of NiCo of the present invention2O4The preparation method of composite material；In molar ratio, hexamethylenetetramine: Co=10-12:1
With taking hexamethylenetetramine.
A kind of NiCo of the present invention2O4The preparation method of composite material；Containing in spirituous aqueous solution；Mole of alcohol and water
Ratio is 0-1:9, preferably 1:9.
A kind of NiCo of the present invention2O4The preparation method of composite material；2000-2500ml is added by 1g cobalt chloride and contains alcohol
The ratio of aqueous solution cobalt chloride, nickel chloride and hexamethylenetetramine are dissolved in containing in spirituous aqueous solution, stirring is to mixed
It closes uniform.
A kind of NiCo of the present invention2O4The preparation method of composite material；The temperature of heating is 90-130 DEG C, preferably 100-120
DEG C, further preferably 120 DEG C.
A kind of NiCo of the present invention2O4The preparation method of composite material；After obtaining green solution, NiCo is generated by theoretical2O4Matter
Graphene and/or graphene oxide is added in the 10-15% of amount thereto.The graphene is few layer graphene；The graphene
The number of plies be less than or equal to 5 layers, the preferably mixture that is made of different layers of graphenes.
A kind of NiCo of the present invention2O4The preparation method of composite material；It is nickel cobalt bimetal hydroxide that gained, which obtains green solution,
Object presoma.
A kind of NiCo of the present invention2O4The preparation method of composite material；Graphene is added in ultrasonic state, graphene adds completely
Continue 10~15min of ultrasonic mixing after entering.The frequency of the ultrasound is 20K-40KHz.
A kind of NiCo of the present invention2O4The preparation method of composite material；Washing is filtered by washing lotion of distilled water；Until
When the concentration of chloride ion is less than or equal to 0.01mol/L in eluate, terminate washing.
A kind of NiCo of the present invention2O4The preparation method of composite material；The drying is vacuum drying, when the vacuum drying,
Air pressure is less than or equal to 0.1Pa in control furnace, control drying time is 5-15h.
A kind of NiCo of the present invention2O4The preparation method of composite material；The temperature of the calcining is 200-350 DEG C, is preferably
250-300 DEG C, further preferably 260 DEG C, calcining time be 1-3h, preferably 1.5-2.5h, further preferably 2h.
A kind of NiCo of the present invention2O4The preparation method of composite material；When from room temperature to calcination temperature, control heating speed
Rate is 1-3 DEG C/min, preferably 2-2.5 DEG C/min, further preferably 2 DEG C/min.
A kind of NiCo of the present invention2O4The application of composite material, including it is used as lithium ion battery negative material.
A kind of NiCo of the present invention2O4It is 1-2 microns by granularity with the application of graphene multistage self-assembled nanometer floral material
NiCo2O4It is used as active cathode material with graphene multistage self-assembled nanometer flower, is prepared into lithium ion battery.
A kind of NiCo of the present invention2O4It is 1-2 microns by granularity with the application of graphene multistage self-assembled nanometer floral material
NiCo2O4It is used as active cathode material with graphene multistage self-assembled nanometer flower, using metal lithium sheet as anode, with the LiF of 1M6
It is dissolved in the EC/DMC that volume ratio is 1:1 and lithium ion battery is made as electrolyte, using polypropylene screen as diaphragm；The lithium from
Reversible lithium storage specific capacity is up to 1206.9mAh g after sub- circulating battery 35 times-1.5000mA g is up in current density-1When
NiCo2O4/ graphene composite material shows 150mAh g-1Stabilization specific capacity, and return to 50mA g when current density-1Shi Qi
Specific discharge capacity may return to and stablize in 1470mAh g-1。
Principle and advantage
Compared with the prior art, the invention has the following advantages:
(1) previous method of modifying is compared by NiCo2O4For nanosizing or carbon coating, this research passes through simple liquid phase
Method synthesizes Ni-Co layered double hydroxide, and one-step calcination of going forward side by side obtains multistage nanostructure by very thin bimetal nano
Thin slice is perfectly adhered on graphene by the effect of Electrostatic Absorption, and the multi-stage nano floral structure of this novelty can be effectively
Stop the self aggregation of two-dimension nano materials；Graphene acts not only as conductive network enhancing NiCo simultaneously2O4The conduction of nanometer sheet
Property, the stress of lithium ion deintercalation generation can also be buffered.
(2) provided by the invention for compared to the negative electrode material graphite theoretical specific capacity 372mAh/g being commercialized at present
NiCo2O4/ graphene composite material has very superior performance, for example, reversible lithium storage specific capacity is up to after circulation 35 times
1206.9mAh g-1, and pure NiCo2O4From initial 1071.1mAh g-1Only 218.2mAh g is rapidly decreased to after circulation 30 times-1；
In addition, being up to 5000mA g in current density-1When NiCo2O4/ graphene composite material shows 150mAh g-1Stabilization ratio
Capacity, and when current density returns to 50mA g-1When its specific discharge capacity may return to and stablize in 1470mAh g-1。
Detailed description of the invention
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 of/graphene composite material schemes；
Fig. 2 (e) is NiCo in embodiment 12O4The TEM of/graphene composite material schemes；
Fig. 2 (f) is NiCo in embodiment 12O4The HTEM of/graphene composite material schemes.
Fig. 3 is NiCo in embodiment 12O4SEM figure.
Fig. 4 (a) is the NiCo of embodiment 12O4SEM figure before/graphene composite material circulation；
Fig. 4 (b) is the NiCo of embodiment 12O4SEM after/graphene composite material recycles 50 times schemes.
Fig. 5 (a) is NiCo in embodiment 22O4The charge and discharge process voltage and specific capacity curve of/graphene composite material；
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 graph
Fig. 5 (f) is NiCo2O4CV curve graph.
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.
From Fig. 1 (a) it can be seen that with pure NiCo2O4Compared to NiCo2O4The diffracting spectrum of/graphene composite material is in 2 θ
To have an apparent amorphous diffraction maximum at 20~30 °, which demonstrate the presence of graphene；It can be seen that temperature from Fig. 1 (b)
Degree is about that 300-450 ° of sharp exothermic peak represents graphene decomposition reaction has occurred and result in 6.88% mass loss i.e.
The content of graphene.
It can be seen that pure NiCo from Fig. 2 (a)2O4For very thin two-dimensional layer；It is from Fig. 2 (b) it can be seen that pure
NiCo2O4The larger nearly micron order of area；It can be seen that high-resolution is mutually typical NiCo from Fig. 2 (c)2O4Striped picture；From Fig. 2
(d) it can be seen that NiCo in2O4/ graphene composite material is in nano flower pattern；It can be seen that NiCo from Fig. 2 (e)2O4With stone
Black alkene combines fine；From can be seen that in Fig. 2 (f) under high-resolution with NiCo2O4Typical striped picture and graphene non-crystal bar
Line picture and the two combine fine.
As can be seen from Figure 3 NiCo2O4For two-dimensional sheet.
NiCo before it can be seen that circulation in Fig. 4 (a)2O4/ graphene composite material is in nano flower-like；From Fig. 4 (b)
It can be seen that the NiCo after 50 circle of circulation2O4Nano flower pattern is still presented in/graphene composite material, in conjunction with Fig. 4 (a), Fig. 4 (b)
In it can be seen that graphene addition facilitate prevent NiCo2O4Volume in cyclic process crushes, and largely maintains
Its pattern.
No. 1 curve indicates NiCo in Fig. 5 (a)2O4The capacity voltage of the 1st charge and discharge of/graphene composite material, No. 2 curves
Indicate NiCo2O4The capacity voltage of the 2nd charge and discharge of/graphene composite material, No. 10 curves indicate NiCo2O4/ graphene is compound
The capacity voltage of the 10th charge and discharge of material, No. 30 curves indicate NiCo2O4The appearance of the 30th charge and discharge of/graphene composite material
Measure voltage；It can be seen that NiCo from Fig. 5 (a)2O4/ graphene composite material is obvious and steady from charging/discharging voltage platform after the 2nd time
Fixed, reversible capacity is higher than 1200mAh g-1。
No. 1 curve indicates NiCo in Fig. 5 (b)2O4The capacity voltage of the 1st charge and discharge of material, No. 10 curves indicate
NiCo2O4The capacity voltage of the 10th charge and discharge of material, No. 30 curves indicate NiCo2O4The capacity electricity of the 30th charge and discharge of material
Pressure；It can be seen that pure NiCo from Fig. 5 (b)2O4Material capacity is lower than 220mAh g after constantly declining 30 circles-1；In conjunction with Fig. 5 (a),
Fig. 5 (b) is it can be seen that NiCo2O4/ graphene composite material constant current charge-discharge performance is much higher than pure NiCo2O4Material.
It can be seen that NiCo from Fig. 5 (c)2O4Reversible capacity is maintained at after 35 circle of/graphene composite material circulation
1206.9mAh g-1；It can be seen that pure NiCo from Fig. 5 (d)2O4Reversible capacity is rapidly decreased to after material circulation 35 times
218.2mAh g-1。
No. 1 curve indicates NiCo in Fig. 5 (e)2O4The CV curve of/graphene composite material first charge-discharge, No. 2 curve tables
Show NiCo2O4The CV curve of the 2nd charge and discharge of/graphene composite material, No. 3 curves indicate NiCo2O4/ graphene composite material
The CV curve of 3rd charge and discharge, No. 4 curves indicate NiCo2O4The CV curve of/graphene composite material the 4th charge and discharge；From Fig. 5
(e) it can be seen that NiCo in2O4In addition to there is amorphous Li for the first time in/graphene composite material2The generation of O and solid electrolyte film is anti-
Should be outer, reaction registration later is very high.
No. 1 curve indicates pure NiCo in Fig. 5 (f)2O4The CV curve of material first charge-discharge, No. 2 curves indicate pure
NiCo2O4The CV curve of the 2nd charge and discharge of material, No. 3 curves indicate pure NiCo2O4The CV curve of the 3rd charge and discharge of material, No. 4
Curve indicates pure NiCo2O4The CV curve of material the 4th charge and discharge；It can be seen that pure NiCo from Fig. 5 (f)2O4Material charge and discharge
It reacts more and more weaker；In conjunction with Fig. 5 (e), Fig. 5 (f) it can be seen that NiCo2O4/ graphene composite material cyclical stability is much higher than pure
NiCo2O4Material.
It can be seen that NiCo from Fig. 6 (a)2O4/ Graphene electrodes are in 100mA g-1It recycles 10 times and maintains under electric current
1207 mAh g-1Reversible capacity, 500mA g-1It is 1038.1mAh g that 10 reversible capacities are recycled under electric current-1, 1000mA g-1
It is 666.3mAh g that 10 reversible capacities are recycled under electric current-1, 2000mA g-1It is 319.5 that 10 reversible capacities are recycled under electric current
mAh g-1, and 5000mA g-110 reversible capacities are recycled under electric current to remain to maintain 150mAh g-1；When returning once again to
50mA g-1Current density when, reversible capacity can restore and stablize in 1470mAh g-1；It can be seen that from Fig. 6 (b)
NiCo2O4Semicircle diameter be much larger than NiCo2O4Semicircle diameter, that is, NiCo of/graphene2O4Charge-transfer resistance it is higher.
Specific embodiment
It is intended to further illustrate the present invention with reference to embodiments, is not intended to limit the present invention.
Embodiment 1
Weigh the cobalt chloride hexahydrate (CoCl of 0.2379g commercialization2·6H2O), six chloride hydrates of 0.1188g commercialization
Nickel (NiCl2·6H2O), the hexamethylenetetramine (C of 1.6822g commercialization6H12N4), they are dissolved in 200ml and is prepared in advance
According to volume ratio be 9:1 deionized water and dehydrated alcohol (C2H6O2) mixed liquor in；Acquired solution, which is transferred to capacity, is
In the three neck round bottom flask of 500ml, round-bottomed flask is put into the digital display heat collecting type blender equipped with methyl-silicone oil and is stirred
Reaction, setting temperature are 120 DEG C, and the Co (OH) of green can be obtained in furnace cooling after the reaction time is 30min2With Ni (OH)2's
Mixture solution (Ni-Co LDH).Graphene oxide solution (negatively charged) is added in obtained Co by 10% mass percent
(OH)2With Ni (OH)2In mixed solution (positively charged), and it is put into ultrasound 2 times (frequency 40KHz), each 10- in Ultrasound Instrument
15min, to guarantee that graphene oxide and Ni-Co LDH electrostatic self-assembled are sufficiently compound layer by layer；It is filtered with deionized water and alcohol
After washing 4-5 times, obtained filter cake is put into vacuum oven dry；Solid after obtained drying is put into Muffle furnace
260 DEG C of calcining 2h, heating rate are 2 DEG C/min, and cooling to room temperature with the furnace can be obtained NiCo2O4With graphene multistage self assembly
Nanometer floral material.
Embodiment 2
NiCo2O4With graphene active material and acetylene black (conductive agent), PVDF (binder) 7:1.5:1.5 in mass ratio
Ratio mixing, grinding until white PVDF substantially uniformity mixing in the material, be added be about 1/0.2379 mass of PVDF
NMP as solvent and stir；Continue stir about after 24 hours, the active material slurry stirred evenly is uniformly coated on Cu
On foil, it is put in air and moves on to 90 DEG C drying 12 hours in vacuum oven after natural drying to it；Take out dried electrode
Piece and the circular electric pole piece for being diameter about 10mm by its punching；It is assembled to obtain for electric performance test in vacuum glove box
Button cell (using lithium piece as cathode), test its electrical property after placing about 6h liquid complete wetting to be electrolysed after compression. Li/
NiCo2O4Being assembled in the glove box (Mbraum, Germany) for being filled with high-purity argon gas for button cell (2016 model) carries out.
Using metal lithium sheet as to electrode, using polypropylene screen as diaphragm, 1M LiPF6It is dissolved in ethyl carbonate/dimethyl carbonate (EC/
DMC) (1:1, volume ratio) is used as electrolyte, negative electrode material of the material of synthesis as battery.It the charging of lithium ion battery and puts
Electric performance test carries out on blue electrical measurement test system at room temperature, and the voltage range of test is 0-3V reference and Li/Li+.Circulation
Volt-ampere test carries 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
With 30 circle) (b) charge and discharge process voltage and specific capacity curve；Charge and discharge cycles stability curve (c), (d)；1st to the 4th
The CV curve (e) of a circulation, (f).
Fig. 6 is (a) NiCo in embodiment 22O4/ graphene composite material multiplying power (current density unit mA g-1) and (b)
AC impedance curve (NiCo2O4Half circular diameter of/graphene composite material is smaller, pure NiCo2O4Half circular diameter of material is obviously more
Greatly).
Claims (7)
1. a kind of NiCo2O4Composite material, it is characterised in that: the NiCo2O4Composite material is NiCo2O4Pass through with graphene more
Nanometer floral material made of grade self assembly；The nanometer floral material passes through Electrostatic Absorption by stratiform NiCo2O4 and lamellar graphite alkene
And it obtains；Layered graphene accounts for the 5-8% of the nanometer floral material gross mass;
The NiCo2O4Composite material has following step preparation: in molar ratio, the ratio of Co:Ni=2:1, which is matched, takes cobalt chloride and chlorine
Change nickel;In molar ratio, hexamethylenetetramine: Co=10-12:1, with taking hexamethylenetetramine；
It will be dissolved in the cobalt chloride, nickel chloride and the hexamethylenetetramine that take containing in spirituous aqueous solution, be heated to 90-120
DEG C, graphene and/or graphene oxide are added thereto after obtaining green solution, washs after mixing, is dry, calcining, obtaining
To NiCo2O4With graphene multistage self-assembled nanometer floral material；
It is described to contain in spirituous aqueous solution；The molar ratio of alcohol and water is 0-1:9.
2. a kind of NiCo according to claim 12O4Composite material；It is characterized by:
Ratio of the 2000-2500ml containing spirituous aqueous solution is added by cobalt chloride, nickel chloride and six methines in 1g cobalt chloride
Tetramine is dissolved in containing in spirituous aqueous solution, and stirring is to being uniformly mixed.
3. a kind of NiCo according to claim 12O4Composite material；It is characterized by: after obtaining green solution, by theory
Generate NiCo2O4Graphene and/or graphene oxide is added in the 10-15% of quality thereto；The graphene is few layer graphene；
The number of plies of the graphene is less than or equal to 5 layers.
4. a kind of NiCo according to claim 12O4Composite material；It is characterized by: graphene is added in ultrasonic state,
Graphene continues 10 ~ 15 min of ultrasonic mixing after being added completely into；The frequency of the ultrasound is 20K-40KHz.
5. a kind of NiCo according to claim 12O4Composite material；It is characterized by:
Washing is filtered by washing lotion of distilled water；Until the concentration of chloride ion is less than or equal to 0.01 mol/L in eluate
When, terminate washing；
The drying is vacuum drying, when the vacuum drying, controls air pressure in furnace and is less than or equal to 0,1Pa, control drying time
For 5-15 h；
The temperature of the calcining is 200-350 DEG C, the time of calcining is 1.5-2.5h；When from room temperature to calcination temperature, control
Heating rate processed is 1-3 DEG C/min.
6. a kind of NiCo described in -5 any one according to claim 12O4Composite material；It is characterized by: prepared by it
NiCo2O4Application with graphene multistage self-assembled nanometer floral material includes being used as lithium ion battery negative material.
7. NiCo described in -5 any one according to claim 12O4The application of composite material, it is characterised in that: by granularity be 1-2
The NiCo of micron2O4It is used as active cathode material with graphene multistage self-assembled nanometer flower, 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 diaphragm, lithium ion battery is made；
Reversible lithium storage specific capacity is up to 1206.9 mAh g after the lithium ion battery recycles 35 times-1；5000 mA are up in current density
g-1When NiCo2O4/ graphene composite material shows 150 mAh g-1Stabilization specific capacity, and return to 50 mA when current density
g-1When its specific discharge capacity may return to and stablize in 1470 mAh g-1。
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