CN107140696B - A kind of plasma fortified oxidizing roasting device for the nickelic positive electrode of synthesizing lithium ion battery - Google Patents

A kind of plasma fortified oxidizing roasting device for the nickelic positive electrode of synthesizing lithium ion battery Download PDF

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CN107140696B
CN107140696B CN201710380474.7A CN201710380474A CN107140696B CN 107140696 B CN107140696 B CN 107140696B CN 201710380474 A CN201710380474 A CN 201710380474A CN 107140696 B CN107140696 B CN 107140696B
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positive electrode
atmospheric pressure
tube furnace
plasma discharge
oxygen
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CN107140696A (en
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应皆荣
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Ningbo University of Technology
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Ningbo University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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 discloses a kind of plasma fortified oxidizing roasting devices for the nickelic positive electrode of synthesizing lithium ion battery, and the plasma fortified oxidizing roasting device includes quartz tube furnace and atmospheric pressure plasma discharge generating device；The quartz tube furnace includes quartz ampoule, the air inlet pipe positioned at described quartz ampoule one end, positioned at the exhaust pipe of the quartz ampoule other end；The atmospheric pressure plasma discharge generating device includes high voltage power supply and the atmospheric pressure plasma discharge generator that is built in the quartz tube furnace；Quartz tube furnace furnace inner gas pressure described in reaction process keeps normal pressure.The present apparatus is of great significance to the comprehensive performance for improving nickelic positive electrode, especially to the cationic mixing degree for reducing nickelic positive electrode, improves the cycle performance and high rate performance of material, and reducing material alkalinity and improving material processing performance has remarkable result.

Description

A kind of plasma fortified oxidation for the nickelic positive electrode of synthesizing lithium ion battery Calciner
Technical field
The invention belongs to technical field of energy material preparation, in particular to a kind of nickelic positive electrode of lithium ion battery etc. Gas ions enhanced oxidation method of roasting.
Background technique
With the fast development of the related industries such as portable electronic product and new-energy automobile, the market of lithium ion battery is needed Rapid growth is asked, the also rapid growth therewith of the demand to positive electrode.
Nickelic positive electrode is often referred to the relatively high layered cathode material of nickel content, including ternary nickle cobalt lithium manganate (presses nickel The ratio of cobalt manganese has 622 types, 701515 types, 811 types etc.), the formula of nickel cobalt lithium aluminate NCA and various doping and modifications it is numerous Material.The advantages of high-nickel material be material specific capacity and energy density it is relatively high, this advantage of the higher material of nickel content It is more prominent, it is considered to be the ideal positive electrode of lithium ion battery with high energy density.
The condition for synthesizing nickelic positive electrode is harsher, one of them important reason is the Ni in calcination2+Than Relatively being difficult to complete oxidation is Ni3+, lead to part Ni2+And Li+Generate mixing, a small amount of Ni2+Occupy Li+Position, will serious shadow The chemical property for ringing material causes specific capacity decline, cycle performance to deteriorate, high rate performance reduction.
To promote Ni2+Oxidation, reduce ion mixing degree, purity oxygen (O is passed through when usually requiring that roasting2).This aspect The cost of oxygen processed is increased, and very high requirement is proposed to the oxidation resistance of stove.Simultaneously because the activity of oxygen is not It is enough strong, only have very small part really to take part in oxidation, most of emission loss in vain in pure oxygen in fact.Due to oxygen Activity it is not strong enough, even being roasted under pure oxygen atmosphere, Ni2+It can not be fully oxidized, ion mixing problem does not obtain It thoroughly solves, further increasing for material electrochemical performance is restricted.Since lithium carbonate can decomposite titanium dioxide in roasting Carbon has certain reproducibility, is unfavorable for Ni2+Oxidation, therefore when prepared by high-nickel material need using lithium hydroxide rather than Lithium carbonate.The cost of lithium hydroxide is higher than lithium carbonate, and odorous and corrosivity, causes worker's working condition severe, saggar Severe life time reduction.
In view of ozone (O under room temperature3) oxidability it is very strong, people once synthesis high-nickel material stove on connected it is smelly Ozone is passed through in furnace by Oxygen Generator, it is intended to promote Ni using the strong oxidizing property of ozone2+Oxidation, but effect is not obvious.It can It can be due to O2And O3It is all neutral molecule, oxidability at high temperature is not much different.
The method that another kind reduces ion mixing degree is to take rich lithium formula, i.e., excessive lithium source (mistake is added in ingredient Amount 10~15%), pass through Li+A large amount of excess inhibit Ni2+In Li+The occupy-place of position.This method has certain effect, but disadvantage It is fairly obvious.It is that joined excessive lithium source first, leads to increased costs；Followed by excessive lithium remains in positive electrode, Material alkalinity is caused to enhance, properties for follow deterioration.It is usually subsequent that the processes such as washing is also needed to remove remaining lithium, it is not only time-consuming Arduously, can also material property be caused to deteriorate.There is no electro-chemical activity additionally, due to remaining lithium compound, also results in material Specific capacity reduces.Usual lithium matches that high material specific capacity is lower, and cycle performance and high rate performance are preferable；Lithium matches low material Specific capacity is higher, but cycle performance and high rate performance are poor.Therefore, a kind of ideal method is also not by rich lithium formula.
Nonthermal plasma chemistry be the 1960s since in subjects such as physics, chemistry, electronics, vacuum techniques The new branch of science formed on the basis of cross development.Using plasma technology can make substance realize one by absorbing electric energy Serial traditional chemical irrealizable new chemical reaction.Contain height excitation abundant in plasma gas discharge space Molecule, atom and ion, special chemical reaction can be carried out using these high activity groups, had with traditional chemical routes Complete different unique law.
There is a kind of atmospheric pressure flat plasma reactor according of document report, oxygen-containing gas is passed through wherein, in plasma Under body electric discharge, oxygen-containing gas generates a large amount of oxygen active particles, including atom O and ozone O3Equal neutral particles, O+、O2 +、O3 +Equal bands The particle and O of positive charge2 -Etc. negatively charged particle etc..This plasma is passed through in water, hydroxy radical can be generated (OH), there is very strong oxidisability and cracking oxidation rate.This plasma is used for water process, it can be with rapid oxidation Almost all of large biological molecule, organic matter and inorganic matter are decomposed, CO is finally degraded to2、H2O and inorganic salts, it is basic herein On developed a kind of high-level oxidation technology, ballast water for ship advanced oxidation processing, Drinking Water advanced oxidation processing etc. It is applied in field.
It has not yet to see and such technology is applied to the nickelic positive electrode preparation field of lithium ion battery to solve lithium ion The nickelic positive electrode of battery Ni in roasting2+It is difficult to the fully oxidized document report for leading to the cationic higher defect of mixing degree.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of plasma fortified oxygen of anode material for lithium-ion batteries Change method of roasting, overcomes the nickelic positive electrode of lithium ion battery Ni in roasting2+It is difficult to fully oxidized lead to cationic mixing degree Higher defect.The present invention improves the comprehensive performance of nickelic positive electrode.
The present invention solves technological means used by above-mentioned technical problem are as follows:
A kind of enhanced oxidation method of roasting of the nickelic positive electrode of lithium ion battery, which is characterized in that by presoma and lithium Source powder uniformly mixes, and is placed in calciner and is roasted, and is continually fed into oxygen-containing gas, is made by plasma discharge described Oxygen-containing gas generates positively charged active oxygen, synthesizes nickelic positive electrode.
Preferably, the calciner is quartz tube furnace；It is highly preferred that the calciner is the quartz of temperature programmed control Tube furnace.
Further, the enhanced oxidation method of roasting of the above-mentioned nickelic positive electrode of a kind of lithium ion battery, including walk as follows It is rapid:
(1) presoma and lithium source powder are uniformly mixed, is placed in and is connected with atmospheric pressure plasma discharge generating device In the quartz tube furnace；
(2) oxygen-containing gas is passed through into the quartz tube furnace, the gas after reaction is from the quartz tube type fire grate Out, furnace inner gas pressure keeps normal pressure in reaction process；
(3) voltage, frequency, the power for adjusting the atmospheric pressure plasma discharge generating device, make the oxygen-containing gas Plasma discharge occurs in the quartz tube furnace, generates active oxygen；
(4) quartz tube furnace is heated up, heat preservation roasting, the nickelic positive electrode of synthesizing lithium ion battery；
(5) after roasting, 150 DEG C are down to hereinafter, closing the atmospheric pressure plasma discharge generating device to furnace temperature.
Preferably, in the step (1), the lithium source is one or both of lithium hydroxide and lithium carbonate.
Preferably, in the step (2), the oxygen-containing gas be air, oxygen-enriched air or purity oxygen, flow be 0.05~ 5L/min。
Preferably, in the step (3), the atmospheric pressure plasma discharge generating device uses AC power source or pulse Power supply, the voltage are 10~50kV, and the frequency is 1~50kHz, and the power is 100~1000W.
Preferably, in the step (4), the heating rate is 100~400 DEG C/h, and holding temperature is 700~900 DEG C, Calcining time is 4~48h.
In above-mentioned technical proposal, when step (4) heat preservation roasts, the active oxygen that plasma discharge generates effectively is strengthened The solid phase reaction of the oxidation of nickel and presoma and lithium source.
Preferably, in the step (4), the nickelic positive electrode of lithium ion battery is LiNixM1-xO2, wherein 1.0 >=x One or more of >=0.6, M Co, Mn, Al, Mg, Ti, V, Cr, Fe, Cu, Zn, Sr, Y, Zr, including but not limited to LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.90Co0.05Mn0.05O2、LiNi0.80Co0.15Al0.05O2。
In one embodiment, the nickelic positive electrode of the lithium ion battery is nickel cobalt lithium aluminate (molecular formula LiNi0.80Co0.15Al0.05O2, abbreviation NCA).
It further includes using following technical scheme that the present invention, which solves above-mentioned technical problem:
A kind of plasma fortified oxidizing roasting device for the nickelic positive electrode of synthesizing lithium ion battery, including quartz Tube furnace and atmospheric pressure plasma discharge generating device；The quartz tube furnace includes quartz ampoule, is located at the quartz ampoule one The air inlet pipe at end, positioned at the exhaust pipe of the quartz ampoule other end；The atmospheric pressure plasma discharge generating device includes height Voltage source and the atmospheric pressure plasma discharge generator being built in the quartz tube furnace.
Further, the quartz ampoule is placed in quartz tube type firebox, and the quartz tube type firebox is filled equipped with temperature programmed control It sets.
Further, the internal diameter of the quartz ampoule is 50mm.
Further, the atmospheric pressure plasma discharge generator is plate-slab construction, is located in the quartz ampoule Portion and one end of the close air inlet pipe, the atmospheric pressure plasma discharge generator include being located inside the quartz ampoule to put down Row and the top electrode being oppositely arranged and lower electrode are distinguished extraction wire from the top electrode and the lower electrode, are connected to positioned at institute It states in the high voltage power supply outside quartz ampoule.
Further, the top electrode and the lower electrode be long 50mm, width 20mm, thickness 2mm it is anti-oxidant heat-resisting stainless Steel disc, surface cover the Al of purity 99%2O3Ceramics form barrier layer, the long 60mm in the barrier layer, width 25mm, thickness as medium 0.5mm, air-gap separation 5mm.
The presoma and lithium source powder are uniformly mixed to form mixture, are placed in the quartz ampoule central bottom, described big Atmospheric pressure discharge plasma generator is as close as possible to the mixture, to make full use of the plasma of generation.
Basic principle of the invention: the cationic mixing degree in nickelic positive electrode is reduced, it is important to by Ni2+Sufficiently Oxidation, this needs stronger oxidizing atmosphere.Such as roaster and atmospheric pressure plasma discharge generator are connected, will be passed through Oxygen-containing gas in furnace first passes through atmospheric pressure plasma discharge generator, under high voltage electric field effect, neutral atom or molecule In electronics be stripped, generate positively charged O+、O2 +、O3 +Isoreactivity particle, the oxidability of these particles is than oxygen (O2)、 Ozone (O3) and elemental oxygen (O) it is stronger, it is easier to from Ni2+In capture electronics, thus by Ni2+It is oxidized to Ni3+.With this containing big The plasma gas that amount oxygen active particles, oxidability and activity are significantly improved effectively strengthens Ni2+Oxidation and forerunner The solid phase reaction of body and lithium source, so that it may synthesize Ni2+Obtain the low nickelic positive electrode of fully oxidized, cationic mixing degree.
The present invention mainly utilizes the strong of the positively charged active oxygen particle of atmospheric pressure plasma discharge generator generation Oxidation, with roasting stove on simply connect ozone generator be it is entirely different, effect also will significantly much.This Invention is to carry out enhanced oxidation by active oxygen particle positively charged in plasma to solid-phase reactant and promote roasting solid High-level oxidation technology in phase reaction, with aqueous solution mainly using hydroxy radical (OH) is also entirely different.Lithium-ion electric The plasma fortified oxidizing roasting method of the nickelic positive electrode in pond or a kind of new thinking, there is not yet document report.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention connects roaster and atmospheric pressure plasma discharge generator, oxygen-containing in furnace by being passed through Gas first passes through atmospheric pressure plasma discharge generator, dissociates into containing a large amount of oxygen active particles (including O+、O2 +、O3 +Deng) etc. Gas ions effectively strengthen Ni with the gas that this oxidability and activity are significantly improved2+Oxidation and presoma and lithium The solid phase reaction in source can synthesize Ni2+Obtain the low nickelic positive electrode of fully oxidized, cationic mixing degree；
(2) since plasma reaction generates a large amount of oxygen active particles, oxidability and oxidation rate are obviously improved, and are roasted Shi Keyong common air or oxygen-enriched air, no longer has to pure oxygen atmosphere, the cost of oxygen processed is reduced, to atmosphere requirements It significantly reduces；
(3) since plasma reaction generates a large amount of oxygen active particles, oxidability and oxidation rate are obviously improved, nickelic Lithium carbonate can also be used in material when preparing be lithium source, significantly reduces lithium source cost, and working condition is greatly improved, corrosivity It significantly reduces, the saggar service life is obviously prolonged；
(4) since plasma reaction generates a large amount of oxygen active particles, oxidability and oxidation rate are obviously improved, do not have It is necessary that Ni is inhibited using rich lithium formula again2+In Li+The occupy-place of position.Certainly due to lithium readily volatilized loss at high temperature, lithium is still Need to be excessive on a small quantity, general excessive 2~5%.Therefore the dosage of lithium source can substantially reduce, and save cost, and lithium residual is reduced, material Alkalinity weakens, and properties for follow improves, and specific capacity is also promoted；
(5) present invention is of great significance to the comprehensive performance for improving nickelic positive electrode, especially to the nickelic anode of reduction The cationic mixing degree of material improves the cycle performance and high rate performance of material, reduces material alkalinity and improves material processability There can be remarkable result.
Detailed description of the invention
Fig. 1 is the plasma fortified oxidizing roasting structure drawing of device of the present invention.
The corresponding title of each appended drawing reference in figure: 1- quartz ampoule；2- presoma and lithium source；3- high voltage power supply；4- atmosphere Press electro-plasma generator；5- air inlet pipe；6- exhaust pipe.
Specific embodiment
In order to better understand the content of the present invention, it is described further combined with specific embodiments below with attached drawing.Ying Li Solution, these embodiments are only used for that the present invention is further described, rather than limit the scope of the invention.In addition, it should also be understood that, After having read the contents of the present invention, person skilled in art makes some nonessential changes or adjustment to the present invention, still belongs to In protection scope of the present invention.
The present invention is a kind of enhanced oxidation method of roasting of nickelic positive electrode of lithium ion battery, is by presoma and lithium source Powder uniformly mixes, and is placed in calciner and is roasted, and is continually fed into oxygen-containing gas, makes described contain by plasma discharge Carrier of oxygen generates positively charged active oxygen, synthesizes nickelic positive electrode.
The calciner is the quartz tube furnace of temperature programmed control.
Specific embodiment is as follows:
(1) presoma and lithium source powder are uniformly mixed, is placed in and is connected with atmospheric pressure plasma discharge generating device In the quartz tube furnace；
(2) oxygen-containing gas is passed through into the quartz tube furnace, the gas after reaction is discharged from the quartz tube furnace, instead Furnace inner gas pressure keeps normal pressure during answering；
(3) voltage, frequency, the power for adjusting the atmospheric pressure plasma discharge generating device, make the oxygen-containing gas Plasma discharge occurs in the quartz tube furnace, generates active oxygen；
(4) quartz tube furnace is heated up, heat preservation roasting, the nickelic positive electrode of synthesizing lithium ion battery；
(5) after roasting, 150 DEG C are down to hereinafter, closing the atmospheric pressure plasma discharge generating device to furnace temperature.
It combines and is illustrated with plasma fortified oxidizing roasting device shown in FIG. 1 in the present invention:
A kind of enhanced oxidation method of roasting of the nickelic positive electrode of lithium ion battery is roasted in plasma fortified oxidation It burns in device and carries out, the plasma fortified oxidizing roasting device includes quartz tube furnace and atmospheric pressure plasma discharge hair Generating apparatus；The quartz tube furnace includes quartz ampoule 1, the air inlet pipe 5 positioned at described 1 one end of quartz ampoule, is located at the quartz ampoule 1 The exhaust pipe 6 of the other end；The atmospheric pressure plasma discharge generating device includes high voltage power supply 3 and is built in the quartz ampoule Atmospheric pressure plasma discharge generator 4 in formula furnace.
The quartz ampoule 1 is placed in quartz tube type firebox, and the quartz tube type firebox is furnished with temperature programmed control device.
The internal diameter of the quartz ampoule 1 is 50mm.
The atmospheric pressure plasma discharge generator 4 is plate-slab construction, positioned at 1 inside of quartz ampoule and is leaned on One end of the nearly air inlet pipe 5, the atmospheric pressure plasma discharge generator 4 include being located at 1 interior parallel of quartz ampoule And the top electrode being oppositely arranged and lower electrode are connected to described in being located at from the top electrode and the lower electrode difference extraction wire In the high voltage power supply 3 outside quartz ampoule 1.
The top electrode and the lower electrode are the anti-oxidant heat-resistance stainless steel piece of long 50mm, width 20mm, thickness 2mm, surface Cover the Al of purity 99%2O3Ceramics form barrier layer, the long 60mm in the barrier layer, width 25mm, thickness 0.5mm, air gap as medium Spacing is 5mm.
Presoma and 2 powder of lithium source are uniformly mixed to form mixture, are placed in 1 central bottom of quartz ampoule, and the atmosphere presses Electro-plasma generator 4 is as close as possible to the mixture, to make full use of the atmospheric pressure plasma discharge generator 4 to produce Raw plasma.
The plasma fortified oxidizing roasting device operation logic is: oxygen-containing gas is logical with certain flow from air inlet pipe 5 Enter, first passes through atmospheric pressure plasma discharge generator 4 and dissociate into active oxygen, the gas using presoma and lithium source 2, after reaction Body is discharged from exhaust pipe 6.
The device is just combined below, and a kind of nickelic positive electrode of lithium ion battery is further illustrated with specific embodiment Plasma fortified oxidizing roasting method.
Embodiment 1
Weigh 0.1mol presoma Ni0.80Co0.15Al0.05(OH)2With 0.105mol lithium hydroxide LiOHH2O, by forerunner Body and lithium hydroxide powder uniformly mix, and are placed in quartz ampoule and (are placed in the burner hearth of quartz tube furnace).With the stream of 100ml/min Measure be passed through into quartz tube furnace oxygen-containing 90% oxygen-enriched air, quartz tube furnace, furnace gas pressure is discharged in gas after reaction Power keeps normal pressure.Using AC power source, the voltage for adjusting atmospheric pressure plasma discharge generating device is 10kV, frequency is 15kHZ, power 100W make oxygen-containing gas that plasma discharge occur in pipe, generate active oxygen.By quartz tube furnace with The heating rate of 200 DEG C/h rises to 800 DEG C, heat preservation roasting 12h, then cooled to room temperature.Plasma in the process The active oxygen that electric discharge generates effectively strengthens the oxidation of nickel and the solid phase reaction of presoma and lithium source, synthesizes nickelic anode material nickel Cobalt lithium aluminate (molecular formula LiNi0.80Co0.15Al0.05O2, abbreviation NCA).After roasting, 150 DEG C are down to hereinafter, closing to furnace temperature Close atmospheric pressure plasma discharge generator.
Measuring mixing degree cationic in the nickel cobalt lithium aluminate cathode material is about 0.8%, pH 11.20, half electricity of button Pond initial coulomb efficiency (0.1C) 91.0%；0.1C grams of specific capacity 205mAh/g of button half-cell；1C grams of specific volume of aluminum hull full battery Measure 175mAh/g, 300 weeks circulation volume conservation rates 97.5%, 500 weeks circulation volume conservation rates 95.5%.
The cationic mixing degree of the nickelic positive electrode of preparation gained is small, gram specific capacity height, cycle performance and good rate capability, Alkalinity is low, processing performance is good, has excellent comprehensive performance.
Embodiment 2
With pure O2Gas replaces oxygen-containing 90% oxygen-enriched air, and other conditions synthesize nickelic anode material nickel with embodiment 1 Cobalt lithium aluminate.Measuring mixing degree cationic in the nickel cobalt lithium aluminate cathode material is about 0.7%, pH 11.18, half electricity of button Pond initial coulomb efficiency (0.1C) 91.8%；0.1C grams of specific capacity 205mAh/g of button half-cell；1C grams of specific volume of aluminum hull full battery Measure 175mAh/g, 300 weeks circulation volume conservation rates 97.6%, 500 weeks circulation volume conservation rates 95.7%.
The nickelic positive electrode of preparation gained also has excellent comprehensive performance, and performance is slightly better than embodiment 1, but ten taps Closely.Show in the case where plasma fortified oxidizing roasting acts on, since plasma generates a large amount of active oxygens, so that i.e. using oxygen-containing 90% oxygen-enriched air also can achieve pure O2The oxidation effectiveness of gas.Therefore it is made under plasma fortified oxidizing roasting effect Standby nickelic positive electrode is without using pure O2Cost and the rigors to gas can be significantly reduced in gas.
Embodiment 3
Oxygen-containing 90% oxygen-enriched air is replaced with air, other conditions synthesize nickelic anode material nickel cobalt aluminium with embodiment 1 Sour lithium.Measuring mixing degree cationic in the nickel cobalt lithium aluminate cathode material is about 2.5%, pH 11.78, and button half-cell is first Secondary coulombic efficiency (0.1C) 89.8%；0.1C grams of specific capacity 201mAh/g of button half-cell；1C grams of specific capacity of aluminum hull full battery 165mAh/g, 300 weeks circulation volume conservation rates 93.6%, 500 weeks circulation volume conservation rates 90.5%.
The nickelic positive electrode of preparation gained also has preferable comprehensive performance, more weaker than embodiment 1, but also compares and connect Closely.Show in the case where plasma fortified oxidizing roasting acts on, since plasma generates a large amount of active oxygens, so that using air Also it can achieve preferable oxidation effectiveness.When therefore preparing nickelic positive electrode under plasma fortified oxidizing roasting effect Air can be used, cost and the rigors to gas can be significantly reduced.But for obtain performance it is more excellent it is nickelic just Pole material, or it is more preferable using oxygen rich gas.
Embodiment 4
With 0.0525mol lithium carbonate Li2CO3Instead of the 0.105mol lithium hydroxide LiOHH in embodiment 12O, other Part synthesizes nickelic anode material nickel cobalt lithium aluminate with embodiment 1.
Measuring mixing degree cationic in the nickel cobalt lithium aluminate cathode material is about 1.0%, pH 11.40, half electricity of button Pond initial coulomb efficiency (0.1C) 90.0%；0.1C grams of specific capacity 202mAh/g of button half-cell；1C grams of specific volume of aluminum hull full battery Measure 172mAh/g, 300 weeks circulation volume conservation rates 96.5%, 500 weeks circulation volume conservation rates 94.5%.
The nickelic positive electrode of preparation gained also has excellent comprehensive performance, and slightly inferior properties are in embodiment 1, but ten tap Closely.Show in the case where plasma fortified oxidizing roasting acts on, since plasma generates a large amount of active oxygens, so that i.e. using decomposition When can generate reproducibility CO2The lithium source lithium carbonate Li of gas2CO3Also it can achieve lithium hydroxide LiOHH2O is the effect of lithium source Fruit.Therefore preparing nickelic positive electrode under plasma fortified oxidizing roasting effect can be used lithium carbonate Li2CO3For lithium source, Lithium source cost can be significantly reduced, improve working conditions, reduce corrosivity and extend the saggar service life.
Embodiment 5
Weigh 0.1mol presoma Ni0.6Co0.2Mn0.2(OH)2With 0.0525mol lithium carbonate Li2CO3, by presoma and carbon Sour powder for lithium uniformly mixes, and is placed in quartz ampoule and (is placed in the burner hearth of quartz tube furnace).With the flow of 50ml/min to quartz Air is passed through in tube furnace, quartz tube furnace is discharged in the gas after reaction, and furnace inner gas pressure keeps normal pressure.Using pulse electricity Source, adjust atmospheric pressure plasma discharge generating device voltage be 14kV, frequency 1kHZ, power 300W, so that air is existed Plasma discharge occurs in pipe, generates active oxygen.Quartz tube furnace is risen to 900 DEG C with the heating rate of 100 DEG C/h, heat preservation 48h is roasted, then cooled to room temperature.The active oxygen that plasma discharge generates in the process effectively strengthens the oxidation of nickel And the solid phase reaction of presoma and lithium source, synthesize nickelic anode material nickel cobalt manganic acid lithium (molecular formula LiNi0.6Co0.2Mn0.2O2, 622 types).After roasting, 150 DEG C are down to hereinafter, closing atmospheric pressure plasma discharge generator to furnace temperature.
Measuring mixing degree cationic in the nickel-cobalt lithium manganate cathode material is about 0.7%, pH 11.10, half electricity of button Pond initial coulomb efficiency (0.1C) 92.0%；0.1C grams of specific capacity 160mAh/g of button half-cell；1C grams of specific volume of aluminum hull full battery Measure 145mAh/g, 300 weeks circulation volume conservation rates 97.6%, 500 weeks circulation volume conservation rates 95.8%.
The cationic mixing degree of the nickelic positive electrode of preparation gained is small, and (nickel content is lower, therefore capacity is lower than for a gram specific capacity height NCA), cycle performance and good rate capability, alkalinity is low, processing performance is good, has excellent comprehensive performance.
Embodiment 6
Weigh 0.1mol presoma Ni0.8Co0.1Mn0.1(OH)2With 0.105mol lithium hydroxide LiOHH2O, by presoma It is uniformly mixed with lithium hydroxide powder, is placed in quartz ampoule and (is placed in the burner hearth of quartz tube furnace).With the flow of 1L/min to Oxygen-containing 70% oxygen-enriched air is passed through in quartz tube furnace, quartz tube furnace is discharged in the gas after reaction, and furnace inner gas pressure is protected Hold normal pressure.Using AC power source, the voltage for adjusting atmospheric pressure plasma discharge generating device is 20kV, frequency 25kHZ, function Rate is 200W, makes oxygen-containing gas that plasma discharge occur in pipe, generates active oxygen.By quartz tube furnace with 300 DEG C/h's Heating rate rises to 750 DEG C, heat preservation roasting 16h, then cooled to room temperature.Plasma discharge generates in the process Active oxygen effectively strengthens the oxidation of nickel and the solid phase reaction of presoma and lithium source, synthesizes nickelic anode material nickel cobalt manganic acid lithium (molecular formula LiNi0.8Co0.1Mn0.1O2, 811 types).After roasting, 150 DEG C are down to hereinafter, closing atmosphere pressure discharging to furnace temperature Plasma generator.
Measuring mixing degree cationic in the nickel-cobalt lithium manganate cathode material is about 1.2%, pH 11.40, half electricity of button Pond initial coulomb efficiency (0.1C) 90.0%；0.1C grams of specific capacity 200mAh/g of button half-cell；1C grams of specific volume of aluminum hull full battery Measure 165mAh/g, 300 weeks circulation volume conservation rates 95.5%, 500 weeks circulation volume conservation rates 93.6%.
The cationic mixing degree of the nickelic positive electrode of preparation gained is small, gram specific capacity height, cycle performance and good rate capability, Alkalinity is low, processing performance is good, has excellent comprehensive performance.
Embodiment 7
Weigh 0.1mol presoma Ni0.90Co0.05Mn0.05(OH)2With 0.105mol lithium hydroxide LiOHH2O, by forerunner Body and lithium hydroxide powder uniformly mix, and are placed in quartz ampoule and (are placed in the burner hearth of quartz tube furnace).With the flow of 5L/min Oxygen-containing 80% oxygen-enriched air is passed through into quartz tube furnace, quartz tube furnace, furnace inner gas pressure is discharged in the gas after reaction Keep normal pressure.Using the pulse power, the voltage for adjusting atmospheric pressure plasma discharge generating device is 50kV, frequency 50kHZ, Power is 1000W, makes oxygen-containing gas that plasma discharge occur in pipe, generates active oxygen.By quartz tube furnace with 400 DEG C/h Heating rate rise to 700 DEG C, heat preservation roasting 4h, then cooled to room temperature.Plasma discharge generates in the process Active oxygen effectively strengthen the oxidation of nickel and the solid phase reaction of presoma and lithium source, synthesize nickelic anode material nickel cobalt manganic acid lithium (molecular formula LiNi0.90Co0.05Mn0.05O2).After roasting, to furnace temperature be down to 150 DEG C hereinafter, close atmosphere pressure discharging etc. from Daughter generator.
Measuring mixing degree cationic in the nickel-cobalt lithium manganate cathode material is about 1.8%, pH 11.70, half electricity of button Pond initial coulomb efficiency (0.1C) 90.0%；0.1C grams of specific capacity 210mAh/g of button half-cell；1C grams of specific volume of aluminum hull full battery Measure 175mAh/g, 300 weeks circulation volume conservation rates 94.5%, 500 weeks circulation volume conservation rates 92.8%.
The cationic mixing degree of the nickelic positive electrode of preparation gained is small, and gram specific capacity height (nickel content is high, therefore capacity is high) follows Ring performance and good rate capability, alkalinity is lower, processing performance is good, has excellent comprehensive performance.
Explanation is compared below with reference to the embodiment of four prior arts:
Comparing embodiment 1
Plasma producing apparatus is closed, other conditions are identical with embodiment 1, synthesize nickelic anode material nickel cobalt aluminium Sour lithium.
Measuring mixing degree cationic in the nickel cobalt lithium aluminate cathode material is about 4.5%, pH 11.98, half electricity of button Pond initial coulomb efficiency (0.1C) 82.8%；0.1C grams of specific capacity 190mAh/g of button half-cell；1C grams of specific volume of aluminum hull full battery Measure 140mAh/g, 300 weeks circulation volume conservation rates 89.1%, 500 weeks circulation volume conservation rates 80.5%.
The cationic mixing degree of the nickelic positive electrode of preparation gained is larger, and gram specific capacity is low, cycle performance and high rate performance Difference, alkalinity height, poor processability, comprehensive performance significantly reduce.Under no plasma fortified oxidizing roasting effect, using containing It is poor that the oxygen-enriched air of oxygen 90% prepares resulting positive electrode performance.
Comparing embodiment 2
Plasma producing apparatus is closed, changes oxygen-containing 90% oxygen-enriched air into pure O2Gas, other conditions and implementation Example 1 is identical, synthesizes nickelic anode material nickel cobalt lithium aluminate.
Measuring mixing degree cationic in the nickel cobalt lithium aluminate cathode material is about 1.5%, pH 11.58, half electricity of button Pond initial coulomb efficiency (0.1C) 88.8%；0.1C grams of specific capacity 202mAh/g of button half-cell；1C grams of specific volume of aluminum hull full battery Measure 169mAh/g, 300 weeks circulation volume conservation rates 96.1%, 500 weeks circulation volume conservation rates 93.5%.
The comprehensive performance of the nickelic positive electrode of preparation gained is substantially reduced than embodiment 1, but more obvious than comparing embodiment 1 It is better.Under no plasma fortified oxidizing roasting effect, pure O is used2Gas prepare resulting positive electrode performance also compared with It is good.But it, can also the property prepared even if the oxygen-enriched air using oxygen-containing 90% in the case where there is plasma fortified oxidizing roasting to act on Nickelic positive electrode that can be more excellent.
Comparing embodiment 3
Plasma producing apparatus is closed, changes oxygen-containing 90% oxygen-enriched air into air, other conditions and embodiment 1 are complete It is exactly the same, synthesize nickelic anode material nickel cobalt lithium aluminate.
Measuring mixing degree cationic in the nickel cobalt lithium aluminate cathode material is about 9.5%, pH 12.10, half electricity of button Pond initial coulomb efficiency (0.1C) 67.5%；0.1C grams of specific capacity 150mAh/g of button half-cell；1C grams of specific volume of aluminum hull full battery Measure 90mAh/g, 300 weeks circulation volume conservation rates 60.1%, 500 weeks circulation volume conservation rates 50.4%.
The cationic mixing degree of the nickelic positive electrode of preparation gained is very big, and gram specific capacity is very low, cycle performance and forthright again Can be very poor, alkalinity is very high, processing performance is very poor, and comprehensive performance is very poor, it is impossible to be used in lithium ion battery.In no plasma Under enhanced oxidation roasting effect, it is infeasible for preparing nickelic positive electrode using air.
Comparing embodiment 4
Plasma producing apparatus is closed, changes oxygen-containing 90% oxygen-enriched air into pure O2Gas, and first by pure O2Gas is logical It crosses ozone generator and generates ozone, then be passed through stove, other conditions are identical with embodiment 1, synthesize nickelic anode material nickel Cobalt lithium aluminate.
Measuring mixing degree cationic in the nickel cobalt lithium aluminate cathode material is about 1.4%, pH 11.48, half electricity of button Pond initial coulomb efficiency (0.1C) 88.9%；0.1C grams of specific capacity 202mAh/g of button half-cell；1C grams of specific volume of aluminum hull full battery Measure 169mAh/g, 300 weeks circulation volume conservation rates 96.3%, 500 weeks circulation volume conservation rates 93.7%.
The comprehensive performance of the nickelic positive electrode of preparation gained is substantially reduced than embodiment 1, basic one with comparing embodiment 2 It causes.Under no plasma fortified oxidizing roasting effect, ozone generator is connected on stove, pure O is replaced with ozone2Gas Body, effect be not significant.
It can be seen that plasma fortified oxidizing roasting method of the invention is to the comprehensive performance for improving nickelic positive electrode It is of great significance.
Above description is not the limitation to invention, and the present invention is also not limited to the example above.The common skill of the art For art personnel in the essential scope of invention, the variations, modifications, additions or substitutions made also should belong to protection scope of the present invention.

Claims (2)

1. a kind of plasma fortified oxidizing roasting device for the nickelic positive electrode of synthesizing lithium ion battery, feature exist In the plasma fortified oxidizing roasting device includes quartz tube furnace and atmospheric pressure plasma discharge generating device；Institute Stating quartz tube furnace includes quartz ampoule (1), the air inlet pipe (5) for being located at the quartz ampoule (1) one end, is located at the quartz ampoule (1) The exhaust pipe (6) of the other end；The atmospheric pressure plasma discharge generating device includes high voltage power supply (3) and is built in the stone Atmospheric pressure plasma discharge generator (4) in English tube furnace；Quartz tube furnace furnace inner gas pressure described in reaction process Keep normal pressure.
2. a kind of plasma fortified oxidation for the nickelic positive electrode of synthesizing lithium ion battery as described in claim 1 roasts Burn device, which is characterized in that the atmospheric pressure plasma discharge generator (4) is plate-slab construction, is located at the quartz One end of (1) internal and close the air inlet pipe (5) is managed, the atmospheric pressure plasma discharge generator (4) includes being located at institute It states quartz ampoule (1) interior parallel and the top electrode being oppositely arranged and lower electrode, draws respectively from the top electrode and the lower electrode Conducting wire out is connected in the external high voltage power supply (3) of the quartz ampoule (1).
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