CN107437620A - The preparation method of nickelic ternary NCM622 nano-materials - Google Patents

The preparation method of nickelic ternary NCM622 nano-materials Download PDF

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CN107437620A
CN107437620A CN201710590120.5A CN201710590120A CN107437620A CN 107437620 A CN107437620 A CN 107437620A CN 201710590120 A CN201710590120 A CN 201710590120A CN 107437620 A CN107437620 A CN 107437620A
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nano
materials
ncm622
source
nickelic ternary
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何亮
吴黎明
安琴友
周亮
王选朋
罗显德
刘桥
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Guangdong Mayna Technology Co Ltd
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Guangdong Mayna Technology Co Ltd
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    • H—ELECTRICITY
    • H01—BASIC 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—BASIC ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—BASIC 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
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses the preparation method of nickelic ternary NCM622 nano-materials, and a certain amount of lithium source, nickel source, cobalt source and manganese source are weighed by elemental mole ratios, and it is added in ethanol in the lump, forms the solution of transparent and homogeneous；Weigh a certain amount of polyvinylpyrrolidone to be added in resulting solution, magnetic agitation, it is all dissolved；Weigh a certain amount of organic sugar to be added in resulting solution as anti-water absorbing agent, continue to stir, it is all dissolved；Resulting solution, which is transferred in syringe, carries out electrostatic spinning, and nanofiber is received with aluminium foil；Products therefrom is sintered in atmosphere；Products therefrom, in high-temperature calcination, obtains nickelic ternary NCM622 nano-materials in argon atmosphere.Products obtained therefrom of the present invention is formed by the nano wire connected and composed in LiNi0.6Co0.2Mn0.2O2 particles, the material can be as the positive electrode of lithium ion battery, with higher specific capacity and good structural stability, the cyclical stability and high rate performance of anode active material of lithium ion battery are improved.

Description

The preparation method of nickelic ternary NCM622- nano-materials
Technical field
The present invention relates to nanometer material and electrochemical technology field, particularly nickelic ternary NCM622- nano-materials Preparation method, the material can be used as anode active material of lithium ion battery.
Background technology
In recent years, with the development of novel energy and the popularization of smart electric grid system, energy storage system is for New Energy The requirement more and more higher of the construction of source infrastructure, in particular for the energy storage system of power set, such as New energy electric Automobile power cell.In current various energy storage technologies, rechargeable battery is long, good in economic efficiency due to its service life The advantages that and favored by people, such as traditional lead-acid battery, nickel-cadmium cell and Ni-MH battery.However, each is traditional All there are shortcomings and limitations in battery, it is difficult to meet growing energy storage demand.Thus, the exploitation of novel energy storage cell It is extremely urgent with application.
At present, in the novel energy storage cell developed, lithium ion battery because with the long-life, high power capacity, self discharge it is small, Memory-less effect and it is environmentally friendly the features such as and enjoy favor.In anode material for lithium-ion batteries, cobalt acid lithium, LiFePO4 and mangaic acid The positive electrodes such as lithium have been widely studied and have been used successfully in automobile power lithium ion battery.But these positive electrodes are maximum The drawbacks of be that its energy density far can not meet requirement of the current people to pure electric automobile course continuation mileage.And nickelic ternary NCM positive electrodes have higher energy density by comparison, you can effectively lifting electric car is permitted boat mileage, by current new Energy pure electric automobile market is more and more good.In numerous nickelic ternary NCM system materials, LiNi0.6Co0.2Mn0.2O2（With Lower abbreviation NCM622）The advantage of capacity, security and the aspect of cost three is had concurrently, therefore it is a kind of more industrialization prospect Lithium ion power battery cathode material.But NCM622 positive electrodes its structure in charge and discharge process easily deteriorates, and finally leads The problems such as causing material capacity decay and heat endurance to decline to a great extent.To solve this problem, with reference to the uniqueness of monodimension nanometer material Structural advantage, the one-dimensional lithium ion intercalation nickelic ternary layered compound based on a kind of NCM622- nano wires of design construction, The structural stability and high rate performance of lithium ion battery are improved, improves its chemical property.At present, NCM622- nano wires Material has not been reported.
The content of the invention
In order to overcome the disadvantages mentioned above of prior art, it is an object of the invention to provide a kind of nickelic ternary NCM622- nanometers Its preparation method of wire material, its preparation process is simple, and energy consumption is relatively low, and yield is higher, resulting NCM622- nano-materials There is good chemical property as anode material for lithium-ion batteries.
The technical solution adopted for the present invention to solve the technical problems is：The system of nickelic ternary NCM622- nano-materials Preparation Method, comprise the following steps：
1）A certain amount of lithium source, nickel source, cobalt source and manganese source are weighed by elemental mole ratios, it is added in ethanol in the lump, put The magnetic agitation 1-2 h in 40 DEG C of thermostat water baths, form the solution of transparent and homogeneous；
2）Weigh a certain amount of polyvinylpyrrolidone and be added to step 1）In resulting solution, magnetic agitation 8-12 h, make its whole Dissolving；
3）Weigh a certain amount of organic sugar and be added to step 2 as anti-water absorbing agent）In resulting solution, continue to stir 0.5-1 h, make it All dissolvings；
4）By step 3）Resulting solution is transferred in syringe, in positive high voltage 13.0-15.0 kV, negative high voltage 1.0-2.5 kV Under the conditions of carry out electrostatic spinning, with aluminium foil receive nanofiber；
5）By step 4）Products therefrom sinters 2-5 h in atmosphere at 220-360 DEG C；
6）By step 5）Products therefrom high-temperature calcination 12-18 h at 800-1000 DEG C in argon atmosphere, obtain nickelic ternary NCM622- nano-materials.
As a further improvement on the present invention：Step 1）Described lithium source is lithium acetate, lithium citrate, LiCl and KNO3In One kind or its any combination；Described nickel source is nickel acetate（C4H6O4Ni•4H2O）And nickel nitrate（Ni(NO3)2•6H2O）In A kind of or its any combination；Described cobalt source is cobalt acetate（C4H6O4Co•4H2O）And cobalt nitrate（Co(NO3)2•6H2O）In A kind of or its any combination；Described manganese source is manganese acetate（Mn(CH3COO)2）And manganese oxalate（MnC2O4）In one kind or its Any combination；The anti-water absorbing agent of described organic sugar is glucose sugar and one kind of fructose or its any combination.
As a further improvement on the present invention：Step 2）Described polyvinylpyrrolidone（PVP）Molecular weight be 1300000。
As a further improvement on the present invention：Described lithium source, nickel source, cobalt source and manganese source is according to Li:Ni:Co:Mn elements Mol ratio is X:6:2:2 with taking, wherein 10.0≤X≤10.7；Step 1）Li+ ion concentration ranges are 2/25- in the solution 2/15 mol/L。
As a further improvement on the present invention：Step 1）To step 3）Described temperature is 40 DEG C；And step 1）To step 3）Carry out under nitrogen protection.
Nickelic ternary NCM622- nano-materials obtained by above-mentioned improvement, by LiNi0.6Co0.2Mn0.2O2Connected in particle The nano wire of composition is formed, and described nanowire diameter is 100-400 nm.
As a further improvement on the present invention：Described nickelic ternary NCM622- nano-materials are as lithium ion battery The application of positive electrode active materials.
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention combines high-voltage electrostatic spinning technology and the method for atmosphere sintering, by sintering the polyvinylpyrrolidone that is carbonized（Point Son amount is 1300000）, finally give nickelic ternary NCM622- nano-materials.Electro-chemical test and performance characterization are shown, are led to The one-dimensional nano line of this method preparation is crossed by LiNi0.6Co0.2Mn0.2O2Connection composition in particle, and be connected with each other between nano wire The three-dimensional netted material formed, pattern are homogeneous.The structure can allow Li+/e-With continuous three-dimensional diffusion passage, conduction is improved Speed, while increase Li+The contact area of electrode active material and electrolyte in abjection and telescopiny.It is and nanowire supported LiNi0.6Co0.2Mn0.2O2Interior connection between particle, the internal stress of effective buffer electrode material can be played, suppress its In cyclic process in crystal structure micro-crack generation, increase structural stability.The nickelic ternary prepared by the method The capacity, high rate performance and cycle life of lithium ion battery greatly improved in NCM622- nano-materials, solves nickelic ternary Positive electrode the problem of structure easily deteriorates in charge and discharge process, the chemical property of lithium ion battery is greatly optimized.And this The preparation method of invention is simply efficient, and cost is low, pollution-free in building-up process, in the lithium ion based on nickelic tertiary cathode material There is huge development prospect in battery.
Nickelic ternary NCM622- nano-materials prepared by the present invention avoid the harshness of Hydrothermal Synthesiss simulation HTHP Condition, the method being combined only with high-voltage electrostatic spinning technology and atmosphere sintering, the material yield prepared is high, pattern is equal First, excellent performance.
The beneficial effects of the invention are as follows：The present invention mixes lithium source, nickel source, cobalt source and manganese source, simply quiet using high pressure The method that Electrospinning and gas-protecting sintering are combined, prepares that pattern is homogeneous, constitutionally stable nickelic ternary NCM622- Nano-material.It is applied to lithium ion battery, shows the characteristics such as high specific discharge capacity, long circulating and high magnification.In addition, This preparation technology is simple, controllable and efficient, beneficial to Industry Promotion.
Brief description of the drawings
Fig. 1 is the NCM622- nanowire precursors SEM figures of the embodiment of the present invention 1；
Fig. 2 is the NCM622- nano wires SEM figures of the embodiment of the present invention 1；
Fig. 3 is the NCM622- nano wire distribution diagram of element of the embodiment of the present invention 1；
Fig. 4 is the NCM622- particles SEM figures of the embodiment of the present invention 1；
Fig. 5 is the NCM622- particle elements distribution maps of the embodiment of the present invention 1；
Fig. 6 is the NCM622- nano-materials of the embodiment of the present invention 1 and the XRD comparison diagrams (A) of NCM622- granular materials and member Cellulose content test result figure (B)；
Fig. 7 be the embodiment of the present invention 1 NCM622- nano-materials and NCM622- granular materials in 50 mA g-1Current density Lower cycle performance figure compares figure (A) and coulombic efficiency comparison diagram (B)；
Fig. 8 be the embodiment of the present invention 1 NCM622- nano-materials and NCM622- granular materials in 50 mA g-1Current density Lower charging and discharging curve comparison diagram；
Fig. 9 be the embodiment of the present invention 1 NCM622- nano-materials and NCM622- granular materials in 50 mA g-1Current density Lower cycle performance comparison diagram；
Figure 10 is the NCM622- nano-materials and NCM622- granular materials high rate performance comparison diagrams of embodiment 1；
Figure 11 is the NCM622- nano-materials of embodiment 1 and charging and discharging curve under NCM622- granular materials difference current densities Comparison diagram.
Embodiment
In conjunction with brief description of the drawings, the present invention is further described with embodiment：
Embodiment 1：
The preparation method of nickelic ternary NCM622- nano-materials, comprises the following steps：
1）10.5 mmol lithium acetates, 6 mmol nickel acetates, 2 mmol cobalt acetates and 2 mmol manganese acetates are added in the lump In 40.0 mL absolute ethyl alcohols, the h of magnetic agitation 1 makes it all dissolve at 40 DEG C, forms the solution of transparent and homogeneous；
2）Weigh 3.8 g polyvinylpyrrolidones (molecular weight 1300000) and be added to step 1）In resulting solution, magnetic force stirs 8 h are mixed, it is all dissolved；
3）Weigh 0.5 g glucose and be added to step 2）In resulting solution, the h of magnetic agitation 1, it is set all to dissolve；
4）By step 3）Resulting solution is with 0.3 ml h-1Speed be transferred in syringe, in the kV of positive high voltage 14.5, negative high voltage Electrostatic spinning is carried out under conditions of 1.5 kV, nanofiber is received with aluminium foil；
5）By step 4）Products therefrom, which is put in Muffle furnace, carries out pre-sintering, slow with 5 DEG C/min speed under air atmosphere 340 DEG C are warming up to, is incubated 2 h；
6）By step 5）Products therefrom carries out double sintering in air atmosphere, and 900 DEG C are warming up to 10 DEG C/min speed, Then the h of high-temperature calcination 16, nickelic ternary NCM622- nano-materials are obtained.
By taking the nickelic ternary NCM622- nano wires obtained by this example as an example, as illustrated in fig. 1 and 2, resulting nickelic three First NCM622- nano-materials after pre-burning and are respectively provided with homogeneous appearance structure after double sintering.Fig. 3 shows by this class method The nickelic tri- kinds of Elemental redistributions of ternary NCM622- nano-materials Ni, Co and Mn prepared are all very uniform.If Figure 4 and 5 are by forerunner Liquid solution directly carries out the SEM and distribution diagram of element for the NCM622- granular materials that two-step sintering obtains.Such as Fig. 6（A）It is shown, by Nickelic ternary NCM622- nano-materials prepared by such method are mutually pure phase with the thing of NCM622- granular materials.And Fig. 6 （B）Middle ICP test results show that the atomic ratio of tetra- kinds of elements of Li, Ni, Co and Mn in two kinds of materials is sufficiently close to 10：6：2：2.
Nickelic ternary NCM622- nano-materials are as anode active material of lithium ion battery, the assembling of lithium ion battery Remaining step of method is identical with common preparation method.The preparation method of positive plate is as follows, using nickelic ternary NCM622- nanometers Wire material is as active material, and acetylene black is as conductive agent, and Kynoar is as binding agent, active material, acetylene black, poly- four The mass ratio of PVF is 80:10:10；After they are sufficiently mixed in proportion, a small amount of isopropanol is added, grinding is uniform, right The thick electrode slices of about 0.5 mm are pressed on roller machine；The oven drying that the positive plate pressed is placed in 80 DEG C is standby after 24 hours.With concentration For 1.0 mol/cm3LiPF6For solution as electrolyte, its solvent is that mass ratio is 1：1：Ethylene carbonate, the carbonic acid of 1 mixing Dimethyl ester and dimethyl carbonate, and the VC for adding mass fraction Wei 2% ~ 5% makees activator, using metal lithium sheet as negative pole, in 2.8- Electrochemical property test is carried out between 4.4 V.
As shown in FIG. 7 and 8 exemplified by nickelic ternary NCM622- nano-materials, lithium-ion button battery is dressed up, in current density 50 Under mA/g, carry out constant current charge-discharge test result and show, its first discharge specific capacity is held up to 187 mAh/g after 50 circulations Measure conservation rate up to 88%, and its first coulombic efficiency be 84%, the nickelic ternary that its performance is far superior under equal test condition NCM622- granular materials.
As shown in figure 9, under the mA/g of current density 100, the specific discharge capacity of nickelic ternary NCM622- nano-materials 164 mAh/g, 92% are up to respectively with the capability retention after 100 circulations, and nickelic ternary NCM622- granular materials only has 150 mAh/g、63%。
As shown in FIG. 10 and 11, the forthright again and nickelic ternary NCM622- particles of nickelic ternary NCM622- nano-materials Material is compared and has obtained significant increase.
Embodiment 2：
The preparation method of nickelic ternary NCM622- nano-materials, it comprises the following steps：
1）10.7 mmol lithium acetates, 6 mmol nickel acetates, 2 mmol cobalt acetates and 2 mmol manganese acetates are added in the lump In 40.0 mL absolute ethyl alcohols, the h of magnetic agitation 1 makes it all dissolve at 40 DEG C, forms the solution of transparent and homogeneous；
2）Weigh 4.0 g polyvinylpyrrolidones (molecular weight 1300000) and be added to step 1）In resulting solution, magnetic force stirs 11 h are mixed, it is all dissolved；
3）Weigh 0.4 g fructose and be added to step 2）In resulting solution, the h of magnetic agitation 0.5, it is set all to dissolve；
4）By step 3）Resulting solution is with 0.3 ml h-1Speed be transferred in syringe, in the kV of positive high voltage 15.0, negative high voltage Electrostatic spinning is carried out under conditions of 2.5 kV, nanofiber is received with aluminium foil；
5）By step 4）Products therefrom, which is put in Muffle furnace, carries out pre-sintering, slow with 5 DEG C/min speed under air atmosphere 350 DEG C are warming up to, is incubated 3 h；
6）By step 5）Products therefrom carries out double sintering in air atmosphere, and 800 DEG C are warming up to 10 DEG C/min speed, Then the h of high-temperature calcination 18, nickelic ternary NCM622- nano-materials are obtained.
By taking the nickelic ternary NCM622- nano-materials obtained by the present embodiment as an example, the constant current charge and discharge that is carried out under 50 mA/g Electrical test results show that its first discharge specific capacity is up to 185.0 mA/g, and capability retention is 90% after 50 circulations.
Embodiment 3：
1）10.2 mmol lithium acetates, 6 mmol nickel acetates, 2 mmol cobalt acetates and 2 mmol manganese acetates are added in the lump In 40.0 mL absolute ethyl alcohols, the h of magnetic agitation 2 makes it all dissolve at 40 DEG C, forms the solution of transparent and homogeneous；
2）Weigh 3.9 g polyvinylpyrrolidones (molecular weight 1300000) and be added to step 1）In resulting solution, magnetic force stirs 12 h are mixed, it is all dissolved；
3）Weigh 0.8 g glucose and be added to step 2）In resulting solution, the h of magnetic agitation 1, it is set all to dissolve；
4）By step 3）Resulting solution is with 0.3 ml h-1Speed be transferred in syringe, in the kV of positive high voltage 15.0, negative high voltage Electrostatic spinning is carried out under conditions of 2.5 kV, nanofiber is received with aluminium foil；
5）By step 4）Products therefrom, which is put in Muffle furnace, carries out pre-sintering, slow with 5 DEG C/min speed under air atmosphere 360 DEG C are warming up to, is incubated 4 h；
6）By step 5）Products therefrom carries out double sintering in air atmosphere, and 1000 are warming up to 10 DEG C/min speed DEG C, then the h of high-temperature calcination 12, obtains nickelic ternary NCM622- nano-materials.
By taking the nickelic ternary NCM622- nano-materials obtained by the present embodiment as an example, the constant current carried out under 100 mA/g is filled Discharge test shows, its first discharge specific capacity is up to 168 mA/g, and capability retention is up to 95% after 100 circulations.
Embodiment 4：
1）10.6 mmol lithium acetates, 6 mmol nickel acetates, 2 mmol cobalt acetates and 2 mmol manganese acetates are added in the lump In 40.0 mL absolute ethyl alcohols, the h of magnetic agitation 2 makes it all dissolve at 40 DEG C, forms the solution of transparent and homogeneous；
2）Weigh 3.5 g polyvinylpyrrolidones (molecular weight 1300000) and be added to step 1）In resulting solution, magnetic force stirs 8 h are mixed, it is all dissolved；
3）Weigh 0.3 g fructose and be added to step 2）In resulting solution, the h of magnetic agitation 0.5, it is set all to dissolve；
4）By step 3）Resulting solution is with 0.3 ml h-1Speed be transferred in syringe, in the kV of positive high voltage 13.0, negative high voltage Electrostatic spinning is carried out under conditions of 1.5 kV, nanofiber is received with aluminium foil；
5）By step 4）Products therefrom, which is put in Muffle furnace, carries out pre-sintering, slow with 5 DEG C/min speed under air atmosphere 350 DEG C are warming up to, is incubated 4 h；
6）By step 5）Products therefrom carries out double sintering in air atmosphere, and 950 DEG C are warming up to 10 DEG C/min speed, Then the h of high-temperature calcination 14, nickelic ternary NCM622- nano-materials are obtained.
By taking the nickelic ternary NCM622- nano-materials obtained by the present embodiment as an example, the constant current carried out under 200 mA/g is filled Discharge test shows, its first discharge specific capacity is up to 146 mAh/g, and capability retention is up to 89% after the circle of circulation 100.
Embodiment 5：
1）10.2 mmol lithium acetates, 6 mmol nickel acetates, 2 mmol cobalt acetates and 2 mmol manganese acetates are added in the lump In 40.0 mL absolute ethyl alcohols, the h of magnetic agitation 1.5 makes it all dissolve at 40 DEG C, forms the solution of transparent and homogeneous；
2）Weigh 3.7 g polyvinylpyrrolidones (molecular weight 1300000) and be added to step 1）In resulting solution, magnetic force stirs 8 h are mixed, it is all dissolved；
3）Weigh 0.7 g glucose and be added to step 2）In resulting solution, the h of magnetic agitation 1, it is set all to dissolve；
4）By step 3）Resulting solution is with 0.3 ml h-1Speed be transferred in syringe, in the kV of positive high voltage 14.0, negative high voltage Electrostatic spinning is carried out under conditions of 2.0 kV, nanofiber is received with aluminium foil；
5）By step 4）Products therefrom, which is put in Muffle furnace, carries out pre-sintering, slow with 5 DEG C/min speed under air atmosphere 330 DEG C are warming up to, is incubated 5 h；
6）By step 5）Products therefrom carries out double sintering in air atmosphere, and 900 DEG C are warming up to 10 DEG C/min speed, Then the h of high-temperature calcination 12, nickelic ternary NCM622- nano-materials are obtained.
With the nickelic ternary NCM622- nano-materials obtained by the present embodiment, the constant current charge-discharge that is carried out under 500 mA/g Test result shows, its first discharge specific capacity is capability retention after 100 circulations up to 91% up to 129 mAh/g.
Embodiment 6：
1）10.4 mmol lithium acetates, 6 mmol nickel acetates, 2 mmol cobalt acetates and 2 mmol manganese acetates are added in the lump In 40.0 mL absolute ethyl alcohols, the h of magnetic agitation 1.5 makes it all dissolve at 40 DEG C, forms the solution of transparent and homogeneous；
2）Weigh 4.1 g polyvinylpyrrolidones (molecular weight 1300000) and be added to step 1）In resulting solution, magnetic force stirs 9 h are mixed, it is all dissolved；
3）Weigh 0.6 g fructose and be added to step 2）In resulting solution, the h of magnetic agitation 1, it is set all to dissolve；
4）By step 3）Resulting solution is with 0.3 ml h-1Speed be transferred in syringe, in the kV of positive high voltage 15.0, negative high voltage Electrostatic spinning is carried out under conditions of 2.0 kV, nanofiber is received with aluminium foil；
5）By step 4）Products therefrom, which is put in Muffle furnace, carries out pre-sintering, slow with 5 DEG C/min speed under air atmosphere 360 DEG C are warming up to, is incubated 2 h；
6）By step 5）Products therefrom carries out double sintering in air atmosphere, and 850 DEG C are warming up to 10 DEG C/min speed, Then the h of high-temperature calcination 16, nickelic ternary NCM622- nano-materials are obtained.
By taking the nickelic ternary NCM622- nano-materials obtained by the present embodiment as an example, the constant current carried out under 1000 mA/g is filled Discharge test shows, its first discharge specific capacity is up to 121 mAh/g, and capability retention is up to 89% after 100 circulations.
Embodiment 7：
1）10.5 mmol lithium acetates, 6 mmol nickel acetates, 2 mmol cobalt acetates and 2 mmol manganese acetates are added in the lump In 40.0 mL absolute ethyl alcohols, the h of magnetic agitation 1.5 makes it all dissolve at 40 DEG C, forms the solution of transparent and homogeneous；
2）Weigh 4.4 g polyvinylpyrrolidones (molecular weight 1300000) and be added to step 1）In resulting solution, magnetic force stirs 10 h are mixed, it is all dissolved；
3）Weigh 0.3 g glucose and 0.3 g fructose is added to step 2）In resulting solution, the h of magnetic agitation 1, make its complete Dissolve in portion；
4）By step 3）Resulting solution is with 0.3 ml h-1Speed be transferred in syringe, in the kV of positive high voltage 14.5, negative high voltage Electrostatic spinning is carried out under conditions of 2.3 kV, nanofiber is received with aluminium foil；
5）By step 4）Products therefrom, which is put in Muffle furnace, carries out pre-sintering, slow with 5 DEG C/min speed under air atmosphere 340 DEG C are warming up to, is incubated 3 h；
6）By step 5）Products therefrom carries out double sintering in air atmosphere, and 900 DEG C are warming up to 10 DEG C/min speed, Then the h of high-temperature calcination 14, nickelic ternary NCM622- nano-materials are obtained.
By taking the nickelic ternary NCM622- nano-materials obtained by the present embodiment as an example, the constant current carried out under 100 mA/g is filled Discharge test shows, its first discharge specific capacity is up to 191 mAh/g, and capability retention is up to 88% after 50 circulations.
In summary, after one of ordinary skill in the art reads file of the present invention, technique according to the invention scheme and Technical concept makes other various corresponding conversion schemes without creative mental labour, belongs to the model that the present invention is protected Enclose.

Claims (7)

1. the preparation method of nickelic ternary NCM622- nano-materials, comprises the following steps：
1）A certain amount of lithium source, nickel source, cobalt source and manganese source are weighed by elemental mole ratios, it is added in ethanol in the lump, put The magnetic agitation 1-2 h in 40 DEG C of thermostat water baths, form the solution of transparent and homogeneous；
2）Weigh a certain amount of polyvinylpyrrolidone and be added to step 1）In resulting solution, magnetic agitation 8-12 h, make its whole Dissolving；
3）Weigh a certain amount of organic sugar and be added to step 2 as anti-water absorbing agent）In resulting solution, continue to stir 0.5-1 h, make it All dissolvings；
4）By step 3）Resulting solution is transferred in syringe, in positive high voltage 13.0-15.0 kV, negative high voltage 1.0-2.5 kV Under the conditions of carry out electrostatic spinning, with aluminium foil receive nanofiber；
5）By step 4）Products therefrom sinters 2-5 h in atmosphere at 220-360 DEG C；
6）By step 5）Products therefrom high-temperature calcination 12-18 h at 800-1000 DEG C in argon atmosphere, obtain nickelic ternary NCM622- nano-materials.
2. the preparation method of nickelic ternary NCM622- nano-materials according to claim 1, it is characterised in that：Step 1）Described lithium source is lithium acetate, lithium citrate, LiCl and KNO3In one kind or its any combination；Described nickel source is acetic acid Nickel（C4H6O4Ni•4H2O）And nickel nitrate（Ni(NO3)2•6H2O）In one kind or its any combination；Described cobalt source is cobalt acetate （C4H6O4Co•4H2O）And cobalt nitrate（Co(NO3)2•6H2O）In one kind or its any combination；Described manganese source is manganese acetate （Mn(CH3COO)2）And manganese oxalate（MnC2O4）In one kind or its any combination；The anti-water absorbing agent of described organic sugar is glucose Sugar and one kind of fructose or its any combination.
3. the preparation method of nickelic ternary NCM622- nano-materials according to claim 1, it is characterised in that：Step 2）Described polyvinylpyrrolidone（PVP）Molecular weight be 1300000.
4. the preparation method of nickelic ternary NCM622- nano-materials according to claim 1, it is characterised in that：It is described Lithium source, nickel source, cobalt source and manganese source according to Li:Ni:Co:Mn elemental mole ratios are X:6:2:2 with taking, wherein 10.0≤X≤ 10.7；Step 1）Li+ ion concentration ranges are 2/25-2/15 mol/L in the solution.
5. the preparation method of nickelic ternary NCM622- nano-materials according to claim 1, it is characterised in that：Step 1）To step 3）Described temperature is 40 DEG C；And step 1）To step 3）Carry out under nitrogen protection.
It is 6. nickelic obtained by the preparation method of the nickelic ternary NCM622- nano-materials according to claim any one of 1-5 Ternary NCM622- nano-materials, it is characterised in that：By LiNi0.6Co0.2Mn0.2O2The nanometer connected and composed in particle is linear Into described nanowire diameter is 100-400 nm.
7. nickelic ternary NCM622- nano-materials according to claim 6, it is characterised in that：Described nickelic ternary Application of the NCM622- nano-materials as anode active material of lithium ion battery.
CN201710590120.5A 2017-07-19 2017-07-19 The preparation method of nickelic ternary NCM622 nano-materials Pending CN107437620A (en)

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