CN107437620A - The preparation method of nickelic ternary NCM622 nano-materials - Google Patents
The preparation method of nickelic ternary NCM622 nano-materials Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium Ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012298 atmosphere Substances 0.000 claims abstract description 19
- 239000011572 manganese Substances 0.000 claims abstract description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 13
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- 239000002070 nanowire Substances 0.000 claims abstract description 12
- 229910052803 cobalt Inorganic materials 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 11
- 239000005030 aluminium foil Substances 0.000 claims abstract description 10
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 239000002121 nanofiber Substances 0.000 claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000006096 absorbing agent Substances 0.000 claims abstract description 5
- 239000006183 anode active material Substances 0.000 claims abstract description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 4
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- BJHIKXHVCXFQLS-UYFOZJQFSA-N Fructose Natural products OC[C@@H](O)[C@@H](O)[C@H](O)C(=O)CO BJHIKXHVCXFQLS-UYFOZJQFSA-N 0.000 claims description 12
- QAHREYKOYSIQPH-UHFFFAOYSA-L Cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 9
- XIXADJRWDQXREU-UHFFFAOYSA-M Lithium acetate Chemical group [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 9
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N Cobalt(II) nitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N D-Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 239000005715 Fructose Substances 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M Lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N Nickel(II) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229940071257 Lithium acetate Drugs 0.000 claims description 2
- WJSIUCDMWSDDCE-UHFFFAOYSA-K Lithium citrate Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 229940071264 lithium citrate Drugs 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 238000005245 sintering Methods 0.000 description 20
- 238000010792 warming Methods 0.000 description 14
- 239000008187 granular material Substances 0.000 description 10
- AIYYMMQIMJOTBM-UHFFFAOYSA-L Nickel(II) acetate Chemical group [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 8
- 230000004087 circulation Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 125000005909 ethyl alcohol group Chemical group 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 210000004027 cells Anatomy 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- -1 nickel-cadmium Chemical compound 0.000 description 2
- 210000000352 storage cell Anatomy 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N Dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 102000014961 Protein Precursors Human genes 0.000 description 1
- 108010078762 Protein Precursors Proteins 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 238000010192 crystallographic characterization Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 201000002161 intrahepatic cholestasis of pregnancy Diseases 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 230000003340 mental Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
Classifications
-
- 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
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.
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| CN109817974A (en) * | 2019-03-27 | 2019-05-28 | 山东理工大学 | A kind of sodium ion nickel manganese magnesium iron quaternary positive electrode and preparation method thereof |
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| CN111087029A (en) * | 2019-12-20 | 2020-05-01 | 中国电子科技集团公司第十八研究所 | Method for preparing high-specific-capacity NCM622 material by one-step sol-gel method |
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| CN109817974B (en) * | 2019-03-27 | 2022-05-03 | 山东理工大学 | Sodium ion nickel manganese magnesium iron quaternary positive electrode material and preparation method thereof |
| CN111916725A (en) * | 2019-05-08 | 2020-11-10 | 中国石油化工股份有限公司 | Phosphorus-doped lithium battery high-nickel positive electrode material and preparation process thereof |
| CN111087029A (en) * | 2019-12-20 | 2020-05-01 | 中国电子科技集团公司第十八研究所 | Method for preparing high-specific-capacity NCM622 material by one-step sol-gel method |
| CN111430704A (en) * | 2020-03-20 | 2020-07-17 | 蜂巢能源科技有限公司 | Fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material and preparation method and application thereof |
| CN111430704B (en) * | 2020-03-20 | 2022-09-20 | 蜂巢能源科技有限公司 | Fluorocarbon co-doped nickel cobalt lithium manganate positive electrode material and preparation method and application thereof |
| CN113998744A (en) * | 2021-10-29 | 2022-02-01 | 西南交通大学 | High-capacity and high-multiplying-power LiNi0.6Co0.2Mn0.2O2Positive electrode material, preparation method and application |
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