CN109167039A - The method of microstage nucleocapsid tertiary cathode material is received in a kind of preparation of low-temperature self-propagating method - Google Patents

The method of microstage nucleocapsid tertiary cathode material is received in a kind of preparation of low-temperature self-propagating method Download PDF

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CN109167039A
CN109167039A CN201810981082.0A CN201810981082A CN109167039A CN 109167039 A CN109167039 A CN 109167039A CN 201810981082 A CN201810981082 A CN 201810981082A CN 109167039 A CN109167039 A CN 109167039A
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core
preparation
tertiary cathode
cathode material
shell
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温广武
张俊亭
王桢
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Shandong University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—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—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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 belongs to the preparation technical fields of anode material for lithium-ion batteries, specifically provide a kind of low-temperature self-propagating method and prepare nucleocapsid tertiary cathode material mLi [NibCocMnd]O2·nLi1+e[NifCogMnh]1‑eO2(m+n=1, ne=a, mb+n (1-e) f=x (1-a), mc+n (1-e) g=y (1-a), md+n (1-e) h=z (1-a), 0.1≤b≤0.5,0.6≤f≤0.9,0≤e≤0.4) method.This method sequentially includes the following steps: prepares nickelic or rich lithium core first, then prepares core-shell structure tertiary cathode material as core, and final high temperature calcines to obtain final microstage nucleocapsid tertiary cathode material of receiving.According to actual design ratio if preparing multi-layer core-shell structure material, repetition prepares shell.Using the high low nickel system tertiary cathode material of stability as shell, coat that disadvantage is more but the core of the higher nickelic system of capacity or rich lithium system, it prepares by the design to structure and in batches, the material of acquisition will preferably play the high capacity of core and the stability feature of shell.The preparation method is simple and quick, and low energy consumption, does not need extra implant clad strip and carrys out the problems such as cost improves capacitance loss, be it is a kind of practical and can industrial applications method.

Description

The method of microstage nucleocapsid tertiary cathode material is received in a kind of preparation of low-temperature self-propagating method
Technical field
The invention belongs to the preparation technical fields of anode material for lithium-ion batteries, specifically provide a kind of low-temperature self-propagating legal system The method of standby nucleocapsid tertiary cathode material.
Background technique
Lithium ion battery because have many advantages, such as high-energy density, it is light-weight, have extended cycle life it is good extensive with the feature of environmental protection Power supply as portable electronic devices such as mobile phone, laptop, digital cameras.Determine a key of battery energy density Factor is exactly the specific capacity of positive electrode.Compared with commercialized positive pole material of lithium cobalt acid, LiMn2O4, LiFePO4, ternary is just Pole material Li [NixCoyMnz]O2The positive material of extensive prospect is considered to have due to higher reversible capacity and low cost Material.
In tertiary cathode material, since nickel cobalt manganese content is different, structure is numerous, common are NCM111,442,523, 622,811 etc., in addition there are also rich lithium system Li1+a[NixCoyMnz]1-aO2.Wherein the ratio increase of nickel is helped to improve holds than electric discharge Amount, but also lead to serious capacity reduction caused by cationic mixing, surface reaction and structural unstable crack propagation；Cobalt ratio Example increases and is conducive to enhancing structure stability, but brings increased costs；Manganese ratio increase advantageously reduces cost, improves safety Property, but manganese dissolution and disproportionation bring roundtrips to decline；The ratio increase of lithium is conducive to increase specific discharge capacity, but can bring The mixing of lithium nickel and increased costs problem.It can be seen that, for NCM111 material (LiNi1/3Co1/3Mn1/3O2), stability and safety Property highest, but specific discharge capacity is low, for NCM811 material (LiNi0.8Co0.1Mn0.1O2), specific discharge capacity is high, but pacifies Full property is poor, hygroscopic, for rich lithium material, then specific discharge capacity highest, but high rate performance and cycle performance inequality.Therefore how Regulation lithium, nickel, cobalt, ratio, structure and cost between manganese are the key that realize high energy system battery.
Co deposited synthesis ternary material is mainly used at present, and operation is controllable, and processing performance is good, but can bring a large amount of three Useless problem, time instrument are at high cost.On the other hand in order to improve the chemical property of NCM, two kinds of modified methods are generallyd use: (1) it adulterates, by introducing foreign atom come enhancing structure stability；(2) it coats, the metal oxidation of cladding layer on surface Object inhibits the generation of side reaction, and the cycle performance and thermal stability of modified NCM material all make moderate progress, but therewith To increase cost.Therefore how to regulate and control ternary material from process and structure itself and be only realization high-quality tertiary cathode material at a low price Key.
Summary of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the present invention provides a kind of preparation of low-temperature self-propagating method and receives microstage nucleocapsid three The method of first positive electrode, this method is simple and quick, and each element can be reached in the solution to molecular level mixing, can prepare cashier Microstage material, and low energy consumption, can be regulated and controled to reaction by parameter, greatly reduce the synthesis cost of tertiary cathode material, Simultaneously by forming different types of core-shell structure, make to have complementary advantages between nucleocapsid, obtain specific discharge capacity, cyclical stability and The excellent tertiary cathode material of security performance.
Specific technical solution of the present invention is as follows:
The method of microstage nucleocapsid tertiary cathode material is received in a kind of preparation of low-temperature self-propagating method, has following molecular composition: Li1+a [NixCoyMnz]1-aO2, wherein 0≤a≤0.4,0.1≤x≤0.9,0.1≤y≤0.5,0.05≤z≤0.6；It is double using nucleocapsid The composite material of layer or multilayer, core are mainly nickelic system or rich lithium system tertiary cathode material, and shell is mainly low nickel system ternary Positive electrode hinders electrolyte to corrode using its stable shell, and structural formula can also be denoted as: mLi [NibCocMnd]O2·nLi1+e [NifCogMnh]1-eO2, wherein m+n=1, ne=a, mb+n (1-e) f=x (1-a), mc+n (1-e) g=y (1-a), md+n (1-e) h =z (1-a), 0.1≤b≤0.5,0.6≤f≤0.9,0≤e≤0.4.
The method of microstage nucleocapsid tertiary cathode material is received in a kind of preparation of low-temperature self-propagating method, sequentially includes the following steps: (1) system Standby nickelic or rich lithium core: according to stoichiometric ratio by lithium nickel cobalt manganese dissolving metal salts in water, a certain amount of reducing agent is added, It stirs evenly, appropriate ammonium hydroxide is added dropwise and adjusts PH, obtains solution A.Solution A is placed in heating furnace, its combustion is made at 300-700 DEG C It burns, then heat preservation a period of time, taking-up obtain powder B at high temperature, and B is collected and is ground.(2) core-shell structure tertiary cathode is prepared Material: according to stoichiometric ratio by nickel cobalt manganese dissolving metal salts in water, a certain amount of reducing agent is added, stirs evenly, be added dropwise Appropriate ammonium hydroxide adjusts PH, and aging for a period of time, powder B is added, is stirred evenly, solution C is obtained.Solution C is placed in heating furnace In, its burning, heat preservation a period of time are made at 300-700 DEG C, taking-up obtains powder D, D is collected and is ground.Continue high-temperature calcination Obtain final microstage nucleocapsid tertiary cathode material of receiving.(3) preparation of multi-layer core-shell structure material: as described above, according to reality Design proportion repeats (1) and (2) process.
Preferably, which is characterized in that the target tertiary cathode material chemical formula is Li1+a [NixCoyMnz]1-aO2, wherein 0≤a≤0.4,0.1≤x≤0.9,0.1≤y≤0.5,0.05≤z≤0.6.
Preferably, which is characterized in that the core-shell material, core be mainly nickelic system or rich lithium system ternary just Pole material, shell are mainly low nickel system tertiary cathode material, structural formula are as follows: mLi [NibCocMnd]O2·nLi1+e [NifCogMnh]1-eO2, wherein m+n=1, ne=a, mb+n (1-e) f=x (1-a), mc+n (1-e) g=y (1-a), md+n (1-e) h =z (1-a), 0.1≤b≤0.5,0.6≤f≤0.9,0≤e≤0.4.
Preferably, which is characterized in that the lithium nickel cobalt manganese metal salt is acetate, propionate, lactate etc. Acylate or nitrate or its hydrate.
Preferably, the reducing agent is urea or citric acid or amion acetic acid or a variety of mixtures, described Ammonium hydroxide tune PH range is 5.5-9.5.
Preferably, the soak temperature for preparing nickelic or rich lithium core is 600-1000 DEG C, the time For 0.5-5h.
Preferably, the ageing time is 2-48h, and temperature is 20-120 DEG C.
Preferably, the final high temperature calcination time is 5-24h, and temperature is 700-1100 DEG C.
Preferably, the specific surface area of the tertiary cathode material of the final core-shell structure is 0.1-0.8m2/ G, tap density 1.2-2.8g/cm3, D50 is 0.2-5 μm.
Compared with prior art, protrusion benefit of the invention is:
The method of microstage nucleocapsid tertiary cathode material is received in a kind of low-temperature self-propagating method preparation of the invention, using new low temperature from climing Prolong technique, at low temperature, metal salt and reducing agent mixed solution are lighted, self-propagating reaction occurs, then product is subjected to high temperature Target substance can be obtained in heat treatment, greatly shortens the production cycle than coprecipitation, substantially reduces the generation of the three wastes.Urea simultaneously Deng the complex system formed with metal salt, the metallic elements such as lithium, nickel, cobalt, manganese is made to realize that molecular level dissolves each other, the complex system of formation Metal ion is slowly released in burning, is gradually solid phase from liquid phase, other anions are then during heat treatment It is burnt into gas, makes material that nano-micro level scale be presented.
The method of microstage nucleocapsid tertiary cathode material is received in a kind of low-temperature self-propagating method preparation of the invention, using two steps or more Footwork forms the tertiary cathode material of the core-shell structure of required different proportion, low nickel system tertiary cathode generally high with stability Material is shell, and disadvantage is more but the core of the higher nickelic system of capacity or rich lithium system for cladding, by design to structure and It prepares in batches, the material of acquisition will preferably play the high capacity of core and the stability feature of shell, especially nickelic material Nickelic is hygroscopic in material, high surface pH, in rich lithium material the conversion bring of Li2MnO3 it is various corrosion and defect problem all Reduce because there is stable low nickel system ternary material shell protection.
The method of microstage nucleocapsid tertiary cathode material is received in a kind of low-temperature self-propagating method preparation of the invention, and microstage is received in preparation The material specific surface area of scale is larger, and not easy to reunite, is uniformly dispersed, and can play higher specific discharge capacity, possesses high Conservation rate is recycled, high rate performance is also improved, while can quickly be adjusted according to cost and actual needs, is not needed additional Be mixed with the problems such as bringing cost to improve capacitance loss, be it is a kind of practical and can industrial applications method.
Detailed description of the invention
Fig. 1 is 0.1LiNi in case study on implementation 11/3Co1/3Mn1/3O2·0.9Li1.2Ni0.133Co0.133Mn0.534O2Material XRD diagram.
Fig. 2 is 0.1LiNi in case study on implementation 11/3Co1/3Mn1/3O2·0.9Li1.2Ni0.133Co0.133Mn0.534O2Material SEM figure.
Fig. 3 is 0.1LiNi in case study on implementation 11/3Co1/3Mn1/3O2·0.9Li1.2Ni0.133Co0.133Mn0.534O2The 1C of material Circulation figure.
Fig. 4 is 0.3LiNi in case study on implementation 21/3Co1/3Mn1/3O2·0.7LiNi0.8Co0.1Mn0.1O2The XRD diagram of material.
Fig. 5 is 0.3LiNi in case study on implementation 21/3Co1/3Mn1/3O2·0.7LiNi0.8Co0.1Mn0.1O2The charge and discharge for the first time of material Electrograph.
Fig. 6 is 0.3LiNi in case study on implementation 21/3Co1/3Mn1/3O2·0.7LiNi0.8Co0.1Mn0.1O2The 1C of material is recycled Figure.
Specific embodiment
The present invention provides the method that microstage nucleocapsid tertiary cathode material is received in a kind of preparation of low-temperature self-propagating method, illustrates below Invention is further explained for bright specific embodiment.
Embodiment 1
This example first prepares 0.9 part of Li1.2Ni0.133Co0.133Mn0.534O2Rich lithium core, then prepare 0.1 part of LiNi1/3Co1/ 3Mn1/3O2Low nickel system shell, general construction formula be Li1.18Ni0.153Co0.153Mn0.514O2.Claim by the stoichiometric ratio of 9:1:1:4 Prepare the LiNO of 2mol/L3、Ni(NO3)2·6H2O、Co(NO3)2·6H2O and Mn (NO3)2The mixing of (50% aqueous solution) metal salt is molten Liquid 45ml is added the amion acetic acid of 0.6mol, stirs evenly, and ammonium hydroxide is added dropwise and adjusts PH to 9, obtains solution A.Solution A is poured into In crucible, make its burning at 600 DEG C, be then warming up to 900 DEG C, keep the temperature 4h, is taken out after furnace cooling and obtain powder B, B is received Collection grinding.By the LiNO of 3:1:1:1 stoichiometric ratio configuration 0.5mol/L3、Ni(NO3)2·6H2O、Co(NO3)2·6H2O and Mn (NO3)2(50% aqueous solution) metal mixed salt solution 20ml, is added the amion acetic acid of 0.2mol, stirs evenly, and ammonium hydroxide is added dropwise and adjusts PH to 9,60 DEG C of aging 1h, adds powder B, stirs to obtain solution C.Solution C is poured into crucible, at 600 DEG C When make its burning, keep the temperature 1h, take out grinding, obtain powder D, 950 DEG C are then warming up in Muffle furnace, keep the temperature 12h, it is cold with furnace But it takes out afterwards and obtains powder 0.1LiNi1/3Co1/3Mn1/3O2·0.9Li1.2Ni0.133Co0.133Mn0.534O2Material.The XRD of material, SEM test result difference is as shown in Figure 1, 2, it is known that the material of synthesis has high-crystallinity, nano-micro level scale, lithium nickel mixing The features such as degree is small.
Slurry is prepared according to the ratio of mass ratio 80:10:10 with Super P, PVDF after above-mentioned material is dried in vacuo, Coating prepares positive plate on aluminium foil, is then assembled into button cell with metal lithium sheet and is tested for the property, wherein electrolyte is 1mol/L LiPF6EC, DMC and EMC mixed liquor (volume ratio 1:1:1), voltage range be 2.2V ~ 4.8V, nominal specific capacity For 200mAh/g.Test results are shown in figure 3 for the 1C cycle performance of material, and 1C specific discharge capacity is 173.7 mAh/g, 100 circles Capacity retention ratio is 92.97%.It is found that this material has very high specific discharge capacity and good cycle performance.
Embodiment 2
This example first prepares 0.7 part of LiNi0.8Co0.1Mn0.1O2Nickelic core, then prepare 0.3 part of LiNi1/3Co1/3Mn1/3O2 Low nickel system shell, general construction formula be LiNi0.66Co0.17Mn0.17O2。
Claim the LiNO for preparing 1mol/L by 100:80:10:10 stoichiometric ratio3、Ni(CH3COO)2·4H2O、Co (CH3COO)2·4H2O and Mn (NO3)2(50% aqueous solution) metal mixed salt solution 35ml, is added the citric acid of 0.3mol, stirring Uniformly, ammonium hydroxide is added dropwise and adjusts PH to 8.5, obtain solution A.Solution A is poured into crucible, makes its burning at 500 DEG C, then rises Temperature keeps the temperature 2h to 750 DEG C, takes out after furnace cooling and obtains powder B, and B is collected and is ground.It is configured by 3:1:1:1 stoichiometric ratio The LiNO of 0.5mol/L3、Ni(CH3COO)2·4H2O、Co(CH3COO)2·4H2O and Mn (NO3)2(50% aqueous solution) metal salt is mixed Solution 30ml is closed, the citric acid of 0.2mol is added, stirs evenly, ammonium hydroxide is added dropwise and adjusts PH to 8.5,85 DEG C of aging 4h are added Powder B stirs to obtain solution C.Solution C is poured into crucible, its burning is made at 600 DEG C, keeps the temperature 1h, taking-up is ground Mill, obtains powder D, then in tube furnace, is passed through the pure oxygen of flowing, is warming up to 900 DEG C, 12h is kept the temperature in oxygen atmosphere, with It is taken out after furnace is cooling and obtains powder 0.3LiNi1/3Co1/3Mn1/3O2·0.7LiNi0.8Co0.1Mn0.1O2Material.The XRD of material is tested As a result as shown in Figure 4 respectively, it is known that the features such as material of synthesis has high-crystallinity, and lithium nickel mixing degree is small.
Slurry is prepared according to the ratio of mass ratio 80:10:10 with Super P, PVDF after above-mentioned material is dried in vacuo, Coating prepares positive plate on aluminium foil, is then assembled into button cell with metal lithium sheet and is tested for the property, wherein electrolyte is 1mol/L LiPF6EC, DMC mixed liquor (volume ratio 3:7), voltage range be 2.8V ~ 4.3V, charging setting 4.3V constant pressure Charging stage, nominal specific capacity are 180mAh/g.The first charge-discharge curve of material is as shown in figure 5, first discharge specific capacity is 175.1mAh/g, first charge-discharge efficiency %, head effect are relatively high.Test results are shown in figure 6 for 1C cycle performance, 1C electric discharge ratio Capacity is 163.1 mAh/g, and 100 circle capacity retention ratios are 95.27%.It is found that this material specific discharge capacity with higher and good Good cycle performance.
Embodiment 3
This example first prepares 0.6 part of LiNi0.7Co0.15Mn0.15O2Nickelic core, then prepare 0.4 part LiNi0.4Co0.2Mn0.4O2Low nickel system shell, general construction formula be LiNi0.58Co0.17Mn0.25O2。
Claim the LiNO for preparing 1mol/L by the stoichiometric ratio of 100:70:15:153、Ni(CH3COO)2·4H2O、Co (CH3COO)2·4H2O and Mn (NO3)2(50% aqueous solution) metal mixed salt solution 60ml, is added the urea of 0.5mol, and stirring is equal It is even, ammonium hydroxide is added dropwise and adjusts PH to 8, obtains solution A.Solution A is poured into crucible, makes its burning at 500 DEG C, is then warming up to 750 DEG C, 2h is kept the temperature, is taken out after furnace cooling and obtains powder B, B is collected and is ground.It is configured by 100:40:20:40 stoichiometric ratio The LiNO of 1mol/L3、Ni(NO3)2·6H2O、Co(NO3)2·6H2O and Mn (NO3)2(50% aqueous solution) metal mixed salt solution 40ml is added the urea of 0.4mol, stirs evenly, and ammonium hydroxide is added dropwise and adjusts PH to 8,90 DEG C of aging 0.5h add powder B, fill Divide and is uniformly mixing to obtain solution C.Solution C is poured into crucible, its burning is made at 550 DEG C, keeps the temperature 1h, grinding is taken out, obtains Powder D is passed through the pure oxygen of flowing then in tube furnace, is warming up to 800 DEG C, and 12h, furnace cooling are kept the temperature in oxygen atmosphere It takes out afterwards and obtains powder 0.4LiNi0.4Co0.2Mn0.4O2·0.6LiNi0.7Co0.15Mn0.15O2Material.
Slurry is prepared according to the ratio of mass ratio 80:10:10 with Super P, PVDF after above-mentioned material is dried in vacuo, Coating prepares positive plate on aluminium foil, is then assembled into button cell with metal lithium sheet and is tested for the property, wherein electrolyte is 1mol/L LiPF6EC, DMC mixed liquor (volume ratio 3:7), voltage range be 2.8V ~ 4.3V, charging setting 4.3V constant pressure Charging stage, nominal specific capacity are 180mAh/g.The first discharge specific capacity of material is 161mAh/g, and first charge-discharge efficiency is 84.9%, 1C specific discharge capacity are 153.8 mAh/g, and 100 circle capacity retention ratios are 96.17%.
Embodiment 4
This example first prepares 0.5 part of LiNi0.8Co0.1Mn0.1O2Nickelic core, then prepare 0.2 part of LiNi0.6Co0.2Mn0.2O2 Middle nickel system middle layer shell, then prepare 0.3 part of LiNi1/3Co1/3Mn1/3O2Low nickel system shell, general construction formula is LiNi0.62Co0.19Mn0.19O2。
Claim the CH for preparing 2mol/L by the stoichiometric ratio of 100:80:10:103COOLi·2H2O 、Ni(CH3COO)2· 4H2O、Co(CH3COO)2·4H2O and Mn (CH3COO)2·4H2O metal mixed salt solution 25ml, is added the citric acid of 0.4mol, It stirs evenly, ammonium hydroxide is added dropwise and adjusts PH to 8.5, obtains solution A.Solution A is poured into crucible, makes its burning at 550 DEG C, so After be warming up to 750 DEG C, keep the temperature 2h, taken out after furnace cooling and obtain powder B, B is collected and is ground.Based on 100:60:20:20 chemistry Measure the CH than configuring 1mol/L3COOLi·2H2O 、Ni(CH3COO)2·4H2O、Co(CH3COO)2·4H2O and Mn (CH3COO)2·4H2O metal mixed salt solution 20ml, is added the citric acid of 0.35mol, stirs evenly, and ammonium hydroxide is added dropwise and adjusts PH To 7.5,70 DEG C of aging 2h, powder B is added, stirs to obtain solution C.Solution C is poured into crucible, at 600 DEG C When make its burning, keep the temperature 1h, take out grinding, obtain powder D.By 3:1:1:1 stoichiometric ratio configuration 1mol/L's CH3COOLi·2H2O 、Ni(CH3COO)2·4H2O、Co(CH3COO)2·4H2O and Mn (CH3COO)2·4H2The mixing of O metal salt Solution 30ml is added the citric acid of 0.3mol, stirs evenly, and ammonium hydroxide is added dropwise and adjusts PH to 8,70 DEG C of aging 2h add powder D stirs to obtain solution E.Solution E is poured into crucible, its burning is made at 600 DEG C, keeps the temperature 1h, takes out grinding, Obtain powder F.Then in tube furnace, it is passed through the pure oxygen of flowing, 850 DEG C is warming up to, 15h is kept the temperature in oxygen atmosphere, with furnace It is taken out after cooling and obtains 0.3 LiNi of powder1/3Co1/3Mn1/3O2·0.2LiNi0.5Co0.2Mn0.3O2· 0.5LiNi0.8Co0.1Mn0.1O2Material.
Slurry is prepared according to the ratio of mass ratio 80:10:10 with Super P, PVDF after above-mentioned material is dried in vacuo, Coating prepares positive plate on aluminium foil, is then assembled into button cell with metal lithium sheet and is tested for the property, wherein electrolyte is 1mol/L LiPF6EC, DMC mixed liquor (volume ratio 3:7), voltage range be 2.8V ~ 4.3V, charging setting 4.3V constant pressure Charging stage, nominal specific capacity are 180mAh/g.The first discharge specific capacity of material is 168.7mAh/g, first charge-discharge efficiency It is 156 mAh/g for 88.3%, 1C specific discharge capacity, 100 circle capacity retention ratios are 95.33%.
Embodiment 5
This example first prepares 0.6 part of Li1.2Ni0.133Co0.133Mn0.534O2Rich lithium core, then prepare 0.2 part LiNi0.5Co0.2Mn0.3O2Middle nickel system middle layer shell, then prepare 0.2 part of LiNi1/3Co1/3Mn1/3O2Low nickel system shell, summarize Structure formula is Li1.12Ni0.247Co0.187Mn0.446O2。
Claim the LiNO for preparing 1mol/L by the stoichiometric ratio of 9:1:1:43、Ni(NO3)2·6H2O、Co(NO3)2·6H2O With Mn (NO3)2(50% aqueous solution) metal mixed salt solution 60ml, is added the urea of 0.6mol, stirs evenly, and ammonium hydroxide is added dropwise and adjusts PH to 9, obtains solution A.Solution A is poured into crucible, makes its burning at 600 DEG C, is then warming up to 900 DEG C, keeps the temperature 4h, with It is taken out after furnace is cooling and obtains powder B, B is collected and is ground.By the LiNO of 100:50:20:30 stoichiometric ratio configuration 1mol/L3、 Ni(NO3)2·6H2O、Co(NO3)2·6H2O and Mn (NO3)20.35mol is added in (50% aqueous solution) metal mixed salt solution 20ml Urea, stir evenly, ammonium hydroxide be added dropwise and adjusts PH to 7.5,70 DEG C of aging 2h add powder B, stir to obtain molten Liquid C.Solution C is poured into crucible, its burning is made at 600 DEG C, keeps the temperature 1h, grinding is taken out, obtains powder D.By 3:1:1:1ization Learn LiNO of the metering than configuring 1mol/L3、Ni(NO3)2·6H2O、Co(NO3)2·6H2O and Mn (NO3)2(50% aqueous solution) metal Mixed salt solution 20ml is added the urea of 0.25mol, stirs evenly, and ammonium hydroxide is added dropwise and adjusts PH to 8,70 DEG C of aging 2h are added Powder D stirs to obtain solution E.Solution E is poured into crucible, its burning is made at 600 DEG C, keeps the temperature 1h, taking-up is ground Mill, obtains powder F.Then it is warming up to 900 DEG C in Muffle furnace, 12h is kept the temperature in oxygen atmosphere, takes out and obtains after furnace cooling 0.2 LiNi of powder1/3Co1/3Mn1/3O2·0.2LiNi0.5Co0.2Mn0.3O2·0.6 Li1.2Ni0.133Co0.133Mn0.534O2Material.
Slurry is prepared according to the ratio of mass ratio 80:10:10 with Super P, PVDF after above-mentioned material is dried in vacuo, Coating prepares positive plate on aluminium foil, is then assembled into button cell with metal lithium sheet and is tested for the property, wherein electrolyte is 1mol/L LiPF6EC, DMC and EMC mixed liquor (volume ratio 1:1:1), voltage range be 2.2V ~ 4.8V, nominal specific capacity For 200mAh/g.The first discharge specific capacity of material is 215.2mAh/g, first charge-discharge efficiency 84.5%, 1C electric discharge specific volume Amount is 153 mAh/g, and 100 circle capacity retention ratios are 93.69%.
Case recited above is only that preferred embodiment embodiment of the invention is described, and is not defined of the invention Conception and scope of protection can also make various deformation and improvement without departing from the principle of the present invention, these also fall into Within the scope of protection scope of the present invention.

Claims (9)

1. microstage nucleocapsid tertiary cathode material Li is received in a kind of preparation of low-temperature self-propagating method1+a[NixCoyMnz]1-aO2Method, it is special Sign is, sequentially includes the following steps: (1) and prepares nickelic or rich lithium core: is according to stoichiometric ratio that lithium nickel cobalt manganese metal salt is molten In Xie Yushui, a certain amount of reducing agent is added, stirs evenly, appropriate ammonium hydroxide is added dropwise and adjusts PH, obtains solution A；Solution A is placed in In heating furnace, its burning is made when 300-700 is spent, then heat preservation a period of time, taking-up obtain powder B, B collected at high temperature Grinding；(2) prepare core-shell structure tertiary cathode material: according to stoichiometric ratio by nickel cobalt manganese dissolving metal salts in water, be added A certain amount of reducing agent, stirs evenly, and appropriate ammonium hydroxide is added dropwise and adjusts PH, and aging for a period of time, powder B is added, is stirred evenly, Obtain solution C；Solution C is placed in heating furnace, its burning is made when 300-700 is spent, heat preservation a period of time, taking-up obtains powder D is collected and is ground by D；Continue high-temperature calcination and obtains final microstage nucleocapsid tertiary cathode material of receiving；(3) multi-layer core-shell structure material The preparation of material: as described above, according to actual design ratio, (1) and (2) process is repeated.
2. the preparation method of material according to claim 1, which is characterized in that the target tertiary cathode material chemistry Formula is Li1+a[NixCoyMnz]1-aO2, wherein 0≤a≤0.4,0.1≤x≤0.9,0.1≤y≤0.5,0.05≤z≤0.6.
3. the preparation method of material according to claim 1, which is characterized in that the core-shell material, core are mainly Nickelic system or rich lithium system tertiary cathode material, shell is mainly low nickel system tertiary cathode material, structural formula are as follows: mLi [NibCocMnd]O2·nLi1+e[NifCogMnh]1-eO2, wherein m+n=1, ne=a, mb+n (1-e) f=x (1-a), mc+n (1-e) g =y (1-a), md+n (1-e) h=z (1-a), 0.1≤b≤0.5,0.6≤f≤0.9,0≤e≤0.4.
4. the preparation method of material according to claim 1, which is characterized in that the lithium nickel cobalt manganese metal salt is acetic acid Salt, propionate, the acylates such as lactate or nitrate or its hydrate.
5. the preparation method of material according to claim 1, which is characterized in that the reducing agent is urea or citric acid Or amion acetic acid or a variety of mixtures, the ammonium hydroxide tune PH range are 5.5-9.5.
6. the preparation method of material according to claim 1, which is characterized in that described to prepare nickelic or rich lithium core Soak temperature is 600-1000 DEG C, time 0.5-5h.
7. the preparation method of material according to claim 1, which is characterized in that the ageing time is 2-48h, temperature It is 20-120 DEG C.
8. the preparation method of material according to claim 1, which is characterized in that the final high temperature calcination time is 5- For 24 hours, temperature is 700-1100 DEG C.
9. the preparation method of material according to claim 1, which is characterized in that the ternary of the final core-shell structure The specific surface area of positive electrode is 0.1-0.8m2/ g, tap density 1.2-2.8g/cm3, D50 is 0.2-5 μm.
CN201810981082.0A 2018-08-27 2018-08-27 The method of microstage nucleocapsid tertiary cathode material is received in a kind of preparation of low-temperature self-propagating method Pending CN109167039A (en)

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