CN104201378B - Method for preparing high-nickel ternary cathode material of lithium ion battery - Google Patents

Method for preparing high-nickel ternary cathode material of lithium ion battery Download PDF

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CN104201378B
CN104201378B CN201410465355.8A CN201410465355A CN104201378B CN 104201378 B CN104201378 B CN 104201378B CN 201410465355 A CN201410465355 A CN 201410465355A CN 104201378 B CN104201378 B CN 104201378B
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lithium
ternary
lithium ion
oxidant
sodium
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CN104201378A (en
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崔妍
郝振佳
江卫军
文博
李化
李化一
张溪
苏迎春
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Beijing mengguli New Material Technology Co.,Ltd.
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Zhongxinguoan Mengguli Power Supply Technology Co Ltd
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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
    • H01M4/48—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
    • 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
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a method for preparing a high-nickel ternary cathode material of a lithium ion battery. According to the method, under the existence, a lithium source and a nickel-cobalt-manganese hydroxide/a nickel-cobalt-aluminum hydroxide are used as reaction substrates and are calcined in an oxygen atmosphere to prepare the high-nickel ternary cathode material of the lithium ion battery. According to the method, the dependency on high-concentration oxygen in a preparation process can be reduced; by the use of low-concentration oxygen, the oxygen cost can be lowered, and a requirement on the sealing property of calcining equipment is also reduced, so that the cost is lowered; meanwhile, compared with the high-nickel ternary cathode material of the lithium ion battery, which is prepared by the common method, the high-nickel ternary cathode material of the lithium ion battery, which is prepared by the method disclosed by the invention, is higher in circulating performance and higher in specific capacity.

Description

A kind of method for preparing the nickelic tertiary cathode material of lithium ion battery
Technical field
The present invention relates to lithium ion anode material preparation field, more particularly to one kind are just preparing the nickelic ternary of lithium ion battery The method of pole material.
Background technology
Since Sony in 1991 is by lithium ion battery commercialization, lithium ion battery is played in the life of people More and more important effect, it is widely used on the electronic products such as computer, camera, mobile phone and power vehicle now. At present, positive electrode mainly includes the LiCoO with layer structure2, LiNiO2, LiMnO2, LiNi1/3Co1/3Mn1/3O2, LiNi0.5Co0.2Mn0.3O2, LiNi0.8Co0.2O2, the LiMn of spinel structure2O4, LiNi0.5Mn1.5O4, olivine structural LiFePO4Deng.As requirement of the market to energy density is improved constantly, lithium ion battery of the research and development with high power capacity becomes when business It is anxious.
Lithium cobaltate cathode material synthesis is easy, and cycle performance is excellent, and compacted density is high, is to be used for business-like material earliest One of, but due to due to cobalt acid lithium self structure, Li1-xCoO2Deintercalation coefficient M must is fulfilled for M≤0.5, otherwise excessive lithium Deintercalation makes positive electrode internal structure cave in, and capacity declines rapidly, and cycle performance declines, and this structure causes cobalt acid lithium Actual gram volume is only capable of the half for performing to theoretical gram volume, is 140mAh/g or so.
Multicomponent material LiNixCoyMn1-x-yO2, especially the higher multicomponent material of nickel content (x >=0.6) is high with capacity, Circulation is excellent, the advantages of low price, in the prior art, in anode material for lithium-ion batteries, with containing nickel cobalt manganese or nickel To have can lithium ion battery good as the positive electrode of lithium ion battery for the ternary material of three kinds of metallic elements of cobalt aluminum Chemical property, especially, increases with nickel element content therein, and the chemical property increase of lithium ion battery is more notable, therefore, The preparation method that exploitation prepares nickelic ternary material is particularly important.
But high-nickel material synthesis condition is harsh, due to Ni during synthesis2+Generation it is inevitable, its polarizability is less, High symmetric unordered salt structure is easily formed, therefore has part Ni2+Li layers are distributed in, lithium ion mixing phenomenon are produced, and is closed High into product surface residual alkali out, pH is high, therefore battery process is difficult to control.
Therefore in order to improve its performance, using in O2The method of synthetic material in atmosphere, to reduce stoichiometry deviation, carries The chemical property of high positive pole；Also lithium nickel ratio can be improved during synthetic material in addition, makes lithium ion excess, reduce Ar ion mixing occupy-place Generation.Even if but it is existing still to there is significantly lithium ion mixing using the positive electrode synthesized by above two method As causing the irreversible capacity of material to raise, production cost can be increased if being to continue with improving oxygen content.
Exist in prior art and lithium ion battery height is prepared by the method for high-temperature calcination under high-load oxygen atmosphere environment The method of nickel tertiary cathode material, such as Chinese patent CN103280575A, disclose a kind of lithium ion secondary battery anode material Hydroxide nickel cobalt manganese or hydroxy cobalt nickel oxide manganese powder end are pressed one with lithium carbonate powder by the preparation method of nickle cobalt lithium manganate, the method Certainty ratio mixes, then under the high temperature conditions, calcines in oxygen atmosphere, and the product after calcining naturally cools to room temperature, enters after crushing again The process of row cladding, product needed for being obtained, the method need the oxygen atmosphere with high-concentration oxygen when positive electrode is prepared, because This, which has strict requirements to the sealing for being passed through the purity and calciner of oxygen,
But said method is required to atmosphere of the oxygen content more than 90%, and this prepared atmosphere is not only needed to reaction High-purity oxygen is passed through in system, and the air-tightness to consersion unit there are strict requirements, although in the lab can be real The existing preparation condition, but in the industrial production as Equipment is difficult to.
Therefore, need exploitation badly a kind of little to oxygen concentration dependence in prepared atmosphere, and obtained lithium ion battery ternary is high The method for preparing the nickelic positive electrode of lithium ion battery ternary of nickel positive electrode excellent performance.
The content of the invention
In order to solve the above problems, present inventor has performed studying with keen determination, as a result find：Preparing lithium ion battery ternary During nickelic positive electrode, a small amount of inorganic oxidizer is added in reaction system, reaction system can be effectively reduced to atmosphere The dependence of middle elevated oxygen level, can be prepared by the nickelic tertiary cathode material of lithium ion battery in the atmosphere compared with low oxygen content, And the nickelic tertiary cathode material of obtained lithium ion battery has preferable cycle performance and higher specific capacity, therefore, this It is bright when the nickelic positive electrode of ternary is prepared, to introduce oxidant in reaction system, so as to complete the present invention.
It is an object of the invention to provide following aspect：
In a first aspect, the present invention provides a kind of preparation method of the nickelic ternary material of lithium ion cell positive, its feature exists In the method is comprised the following steps：
(1) it is lithium source by the ratio of mole by lithium source and ternary precursor:Ternary precursor=1:1～1.05:1 mixing, Prepared precursor mixture, wherein, the mole of lithium source is with the molar amount of elemental lithium in lithium source, the mole of ternary precursor In terms of the mole sum of all metallic elements in ternary precursor；
(2) oxidant being added in obtained precursor mixture in step (1), being ground, raw mixture is obtained；
(3) raw mixture obtained in step (2) is calcined under oxygen atmosphere, crushes after cooling, sieve.
Second aspect, the present invention said method is also provided, it is characterised in that lithium source described in step (1) selected from lithium carbonate, Lithium hydrate and lithium nitrate.
The third aspect, the present invention also provide said method, it is characterised in that ternary precursor described in step (1) is nickel Cobalt manganese hydroxide or nickel cobalt aluminium hydroxide.
Fourth aspect, the present invention also provide said method, it is characterised in that described in step (1), ternary precursor is selected from NixCoyMn1-x-y(OH)2, wherein, 0.6≤x<1,0<y<0.4, and 0<x+y<1, preferably Ni0.9Co0.05Mn0.05(OH)2、 Ni0.8Co0.1Mn0.1(OH)2、Ni0.7Co0.15Mn0.15(OH)2、Ni0.6Co0.2Mn0.2(OH)2And Ni0.8Co0.15Al0.05(OH)2。
In terms of 5th, the present invention also provides said method, it is characterised in that oxidant described in step (2) is selected from high chlorine Hydrochlorate, hypochlorite, permanganate, bichromate, nitrate and inorganic peroxide.
In terms of 6th, the present invention also provides said method, it is characterised in that oxidant described in step (2) is selected from high chlorine Sour sodium, sodium hypochlorite, sodium permanganate, sodium dichromate, potassium hyperchlorate, postassium hypochlorite, potassium permanganate, potassium dichromate, magnesium perchlorate, Magnesium bichromate, sodium peroxide, potassium peroxide, Magnesium dioxide and ammonium nitrate, preferably sodium perchlorate, sodium hypochlorite, potassium hyperchlorate, Postassium hypochlorite, potassium permanganate, magnesium perchlorate or magnesium bichromate, sodium peroxide, potassium peroxide, Magnesium dioxide and ammonium nitrate.
In terms of 7th, the present invention also provides said method, it is characterised in that in step (2), the weight of addition oxidant is The 1～10% of ternary precursor weight, preferably 3～8%, more preferably 4～6%, such as 5%.
Eighth aspect, the present invention also provide said method, it is characterised in that in step (3), in oxygen atmosphere, oxygen concentration is 85～100%, preferably 90～100%.
In terms of 9th, the present invention also provides said method, it is characterised in that in step (3), calcining heat is 600～1000 DEG C, preferably 700～900 DEG C, such as 800 DEG C.
According to the method that the present invention is provided, have the advantages that：
(1) the method is simple to operate, and raw material is easily obtained；
(2) addition of oxidant is alleviated when preparing the nickelic tertiary cathode material of lithium ion battery to elevated oxygen level atmosphere Rely on；
(3) industrialization is easily realized, improves production efficiency,
(4) the method reduces production cost in terms of raw material and production equipment etc..
Description of the drawings
Fig. 1 is obtained the electron microscope of sample in illustrating embodiment 1；
Fig. 2 is obtained the cyclic curve of sample in illustrating embodiment 1；
Fig. 3 is obtained the cyclic curve of sample in illustrating embodiment 2；
Fig. 4 is obtained the cyclic curve of sample in illustrating embodiment 3；
Fig. 5 is obtained the cyclic curve of sample in illustrating comparative example 1.
Specific embodiment
Below by the present invention is described in detail, the features and advantages of the invention will become more with these explanations For clear, clear and definite.
The present inventor adds oxidant through research discovery when nickelic tertiary cathode material is prepared in reaction system, Dependence of the reactant to rich oxygen content atmosphere when nickelic tertiary cathode material is prepared can be alleviated, can efficiently by Ni2+Turn Turn to Ni3+, make Ni in lithium ion anode material3+Content is dramatically increased, so as to improve using the tertiary cathode material as positive pole Lithium ion battery performance.
According to the first aspect of the invention, there is provided a kind of method for preparing the nickelic tertiary cathode material of lithium ion, the method Comprise the following steps：
Step 1, mole of the molar amount of elemental lithium as lithium source with lithium source, with all metal units in ternary precursor The mole sum of element is calculated as the mole of ternary precursor, is lithium source by the ratio that lithium source and ternary precursor press mole:Three First presoma=1:1～1.05:1 mixing, is obtained precursor mixture.
The present inventor it has been investigated that, when nickel, cobalt, manganese, aluminum and other metallic elements pass through homogeneous precipitation method or other sides Nickel-cobalt-manganese ternary presoma, nickel cobalt aluminum ternary precursor or other ternary precursors made by method, wherein, Determination of multiple metal elements row Row more rule, mixes homogeneous, when the content of nickel element is increased, it is also possible to homogeneous ternary precursor, correspondingly, phase is obtained Than in nickelic tertiary cathode material obtained in high-temperature calcination is directly passed through with raw materials such as lithium source, nickel source, cobalt sources, before above-mentioned ternary Drive body more homogeneous with the distribution of various elements in the nickelic tertiary cathode material of lithium ion obtained in lithium source reaction, the arrangement of atom It is more regular, and lithium ion battery is exactly based on deintercalation of the lithium ion on positive and negative pole material and enters embedding, constantly circulation is so as to realizing The recharging effect of lithium ion battery, therefore, the structure of positive electrode is more regular, and Elemental redistribution is more homogeneous, its electrochemistry Can be more stable, also beneficial to improving its specific capacity and cycle performance, therefore, the present invention select with the presoma of tertiary cathode material and Lithium source prepares the nickelic tertiary cathode material of lithium ion battery as reaction raw materials.
Due to containing nickel, cobalt, three kinds of elements of manganese or containing nickel, cobalt, three kinds of elements of aluminum the nickelic ternary of lithium ion battery just Pole strong mechanical property, and the chemical property such as specific capacity is good, therefore, the present invention is preferably with nickel cobalt manganese hydroxide or nickel cobalt aluminum Hydroxide is used as the ternary precursor for preparing the nickelic tertiary cathode material of lithium ion.
The present invention is not specially limited to the mol ratio of three kinds of metallic elements in ternary precursor used, with actual production In can prepare or the nickelic tertiary cathode material electrochemical performance of obtained lithium ion is preferred, preferably chemical formula is NixCoyMn1-x-y(OH)2Ternary precursor, wherein, 0.6≤x<1,0<y<0.4, and 0<x+y<1, such as Ni0.9Co0.05Mn0.05 (OH)2、Ni0.8Co0.1Mn0.1(OH)2、Ni0.7Co0.15Mn0.15(OH)2、Ni0.6Co0.2Mn0.2(OH)2、Ni0.8Co0.15Al0.05 (OH)2Deng.
The present invention is also not specially limited to the source of ternary precursor used, can be voluntarily to prepare, it is also possible to For the available ternary precursor of any one commercially available, the such as model 90505 of Foshan BOUMPLE circulation Science and Technology Ltd. production The production of type, 811 types, the nickel cobalt manganese hydroxide of 622 types, 830 type nickel cobalt aluminium hydroxides and SUMITOMO CHEMICAL KCC 701515 type of model nickel cobalt manganese hydroxide.
The lithium source selected in the present invention is the lithium-containing compound that can decompose at high temperature, such as lithium carbonate, Lithium hydrate and Lithium nitrate etc., these lithium-containing compounds can be decomposed into lithium ion and corresponding gas-phase product at high temperature, wherein, decomposition is obtained Lithium ion and ternary precursor react, and remaining element is then with gaseous substance, such as carbon dioxide, water vapour or nitrogen dioxide etc. Form escapes reaction system, and the nickelic tertiary cathode material of corresponding lithium ion battery is finally obtained.
When the mole of elemental lithium and other metallic elements in the nickelic tertiary cathode material of lithium ion battery mole it The ratio of sum is 1:When 1, the chemical property of the positive electrode is optimal state, due to other metallic elements in the positive electrode Ternary precursor is mostly come from, therefore, when the nickelic tertiary cathode material of lithium ion is prepared, the present invention selects to be relatively easy to obtain The lithium source for obtaining is slightly excessive relative to ternary precursor, i.e. select lithium source to be lithium source with the ratio of the mole of ternary precursor:It is nickelic Ternary material precursor=1:1～1.05:1, when lithium source is more than 1.05 with the ratio of the mole of ternary precursor:When 1, lithium source is big Amount is excessive, causes the waste of lithium source, and the chemical property of the nickelic positive electrode of obtained lithium ion battery also decrease； When lithium source is less than 1 with the ratio of the mole of ternary precursor:When 1, lithium source consumption is not enough, the nickelic positive pole of obtained lithium ion battery Lack enough lithiums in material in positive and negative storeroom deintercalation and enter embedding, cause its chemical property to reduce, wherein, lithium source mole , with the molar amount of elemental lithium in lithium source, the mole of nickelic ternary material precursor is with institute in nickelic ternary material precursor for amount There is the mole sum meter of metallic element.
Step 2, in step 1 adds oxidant in obtained precursor mixture, grinds, raw mixture is obtained.
In prior art, to make reaction raw materials be combined to the nickelic tertiary cathode material of homogeneous lithium ion battery, and which is made In nickel farthest exist with trivalent form, generally using reaction raw materials are calcined in high-purity oxygen atmosphere high temperature On the one hand method, the high-purity oxygen atmosphere required for the method require that the oxygen being passed through in experimental furnace has higher purity, At least need to make the purity of oxygen reach more than 90%；On the other hand require that experimental furnace has good seal, it is anti-to ensure Reaction system is mixed into without other impurity gases during answering, and high-purity oxygen is higher than the manufacturing cost of low-purity oxygen, and And the strict demand to consersion unit seal, also cause the increase of production cost, therefore, lithium ion is prepared using traditional method The nickelic tertiary cathode material of battery, needs higher Financial cost.
And the present inventor it has been investigated that, some have inorganic oxidizer of strong oxidizing property for example perchlorate, hypochlorite, Permanganate, bichromate, nitrate and inorganic peroxide etc., they can be in lithium source and ternary precursor course of reaction In, under the high temperature conditions, promote the carrying out of synthetic reaction, and the nickel element in ternary precursor can be promoted to be converted by bivalence For trivalent, and dependence of the raw material to the high oxygen concentration in reaction environment can be reduced, i.e. the oxygen compared with low-purity can be used Gas, i.e. oxygen purity only need 85%, therefore, oxygen sheet not only can be reduced using oxidant is added in reaction system The cost of body, and, with the reduction required to experimental furnace seal, the cost in terms of consersion unit also greatly can drop It is low, therefore, significantly reduced using the production cost that the nickelic tertiary cathode material of lithium ion battery is prepared after oxidant.
Model HY- of the experimental furnace used in laboratory, such as Hunan Hua Ye microwaves Science and Technology Ltd. production The experimental furnace of SM1500, after evacuation process twice is carried out in advance, then is passed through pure oxygen solid/liquid/gas reactions, measures oxygen purity in tail gas It is 92% for oxygen purity in 92%, i.e. reaction atmosphere, therefore, oxygen in reaction atmosphere can be realized in laboratory scale experiments stove Gas purity reaches 85%, even up to 90%；And in technical grade production, the experimental furnace air-tightness for being used is far below laboratory Used in experimental furnace, the such as experimental furnace of model XD-1200NT of the talented Electric Appliance Equipment Co., Ltd in Zhengzhou production, when to When being wherein passed through purity oxygen, have large quantity of air and be mixed into wherein, oxygen purity is 86% in measuring tail gas, i.e., industrially realize In reaction atmosphere, oxygen purity reaches 90% and is difficult to, and it is easily to realize that in reaction atmosphere, oxygen purity reaches 85%, Therefore, in reaction atmosphere, oxygen purity is reduced to 85% with significant industrial applicibility by 90%, referring specifically to 1 He of experimental example Experimental example 2.
In anode material for lithium-ion batteries, existing on a small quantity for some metallic elements such as Na elements, K element or Mg elements is right The performance of anode material for lithium-ion batteries does not result in negative effect, it might even be possible to lift its performance, and some cationes such as NH4 + Deng, which can be decomposed into gas under the high temperature conditions, so as to escape reaction system, therefore, selective oxidation agent of the present invention is by Na+、K+、Mg2+Perchlorate, hypochlorite with the formation of perchlorate, hypochlorite, MnO4 or dichromate ion, permanganic acid Salt or bichromate, such as sodium perchlorate, sodium hypochlorite, sodium permanganate, sodium dichromate, potassium hyperchlorate, postassium hypochlorite, permanganic acid Potassium, potassium dichromate, magnesium perchlorate or magnesium bichromate；Or be sodium peroxide, potassium peroxide and Magnesium dioxide, or be in high temperature Under can be analyzed to the ammonium nitrate of gas.
In presoma, manganese element is present with+4 valency forms, and Mn4+/Mn7+Electric potential difference be about 1.69eV, and above-mentioned oxygen Therefore, the oxidisability of above-mentioned oxidant is not enough to for manganese element to be oxidized to+7 valencys by+4 valencys agent, its final obtained lithium from Still exist with+4 valencys in the nickelic tertiary cathode material of sub- battery.
Above-mentioned oxidant can be under conditions of the nickelic tertiary cathode material of lithium ion be prepared by the nickel unit in presoma Element is oxidized to trivalent by bivalence, meanwhile, manganese element will not be oxidized to+7 valencys by+4 valencys again, but above-mentioned bichromate is poisonous Property, and for save production cost, preferred oxidant of the present invention be sodium perchlorate, sodium hypochlorite, potassium hyperchlorate, postassium hypochlorite, Potassium permanganate, magnesium perchlorate or magnesium bichromate, sodium peroxide, potassium peroxide, Magnesium dioxide and ammonium nitrate.
The present inventor's research finds, when the weight for adding oxidant is more than the 10% of ternary precursor weight, oxidant Consumption it is excessive, excessive oxidant not only increases production cost, though and introduce sodium, potassium or magnesium elements when a small amount of to system The positive electrode for obtaining is without negative effect, but introduction volume excessively will also result in the chemical property decline of positive electrode；And when addition When the weight of oxidant is less than the 1% of ternary precursor weight, oxidizer is too small, and its Oxidation to reactant is not Foot, the nickel element in presoma can not be converted into+trivalent by+divalent completely, cause obtained positive electrode chemical property lifting Not significantly, therefore, it is the 1%～10% of ternary precursor weight that the present invention selects to add the weight of oxidant, preferably 3～ 8%, more preferably 4～6%, such as 5%.
Step 3, raw mixture obtained in step 2 is calcined under oxygen atmosphere, crushes, sieve after cooling.
The present invention in the atmosphere that oxygen concentration is more than 85%, preferably oxygen concentration be more than 90% atmosphere in calcine Lithium source can be made to react with ternary precursor, and nickel element therein is oxidized to into+trivalent, make the nickelic ternary of lithium ion battery Positive electrode.
When calcining heat is more than 600 DEG C, reaction is quick, and the nickelic tertiary cathode material of obtained lithium ion battery is equal It is even, stable electrochemical property, be it is cost-effective, preferred calcination temperature of the present invention be 600～1000 DEG C, preferably 700～900 DEG C, such as 800 DEG C.
Product can be crushed to into different particle diameters according to the different needs of product.
Embodiment
In the present embodiment and comparative example, experimental furnace used is technical grade experimental furnace, is the talented Electric Appliance Equipment Co., Ltd in Zhengzhou The experimental furnace of model XD-1200NT of production；
Ternary precursor Ni used0.8Co0.1Mn0.1(OH)2The model of Science and Technology Ltd.'s production is circulated for Foshan BOUMPLE 811 ternary precursor；
Ternary precursor Ni used0.8Co0.15Al0.05(OH)2The model of Science and Technology Ltd.'s production is circulated for Foshan BOUMPLE For 830 ternary precursor；
Ternary precursor Ni used0.7Co0.15Mn0.15(OH)2For the model of SUMITOMO CHEMICAL KCC production 701515 ternary precursor.
In experimental example, technical grade experimental furnace used is model XD- of the talented Electric Appliance Equipment Co., Ltd's production in Zhengzhou The experimental furnace of 1200NT；Laboratory scale experiments stove used is model HY- of Hunan Hua Ye microwaves Science and Technology Ltd. production The experimental furnace of SM1500.
Embodiment 1
(1) Li in molar ratio：(Ni+Co+Mn)=1.02:1 by Lithium hydrate and nickel cobalt manganese hydroxide Ni0.8Co0.1Mn0.1(OH)2Mixing, wherein Ni0.8Co0.1Mn0.1(OH)2Quality be 100g, be obtained precursor mixture,
(2) addition potassium permanganate 5g, ball milling, the roasting in oxygen atmosphere at a temperature of 780 DEG C in precursor mixture 20h, obtains nickel cobalt manganese lithiated compound,
(3) will crush after the cooling of nickel cobalt manganese lithiated compound, cross 300 mesh sieves and obtain product LiNi0.8Co0.1Mn0.1O2, its sulfur Acid group content is 2800ppm, and the D50 of granularity is 10.6 μm.
With resulting material as positive pole, with lithium piece as negative pole, button cell is assembled into, in the voltage model of 3.0～4.3V Interior discharge and recharge is enclosed, the specific capacity of reversible discharge first for measuring the material is 172.3mAh/g, and 50 times circulation conservation rate is 97.5%, Its scanning electron microscope (SEM) photograph is as shown in figure 1, cyclic curve is as shown in Figure 2.
Embodiment 2
(1) Li in molar ratio：(Ni+Co+Al)=1.01:1 by Lithium hydrate and nickel cobalt manganese hydroxide Ni0.8Co0.15Al0.05(OH)2Mixing, wherein Ni0.8Co0.15Al0.05(OH)2Quality be 200g, be obtained precursor mixture,
(2) ammonium nitrate 10g, ball milling, with roasting in oxygen atmosphere at a temperature of 800 DEG C are added in precursor mixture 20h, obtains nickel cobalt aluminum lithiated compound,
(3) crush after cooling down, cross 300 mesh sieves and obtain product LiNi0.8Co0.15Al0.05O2, its sulfate radical content is 2660ppm.
With resulting material as positive pole, with lithium piece as negative pole, button cell is assembled into, in the voltage model of 3.0～4.3V Interior discharge and recharge is enclosed, the specific capacity of reversible discharge first for measuring the material is 173.3mAh/g, and 50 times circulation conservation rate is 97.1%, Its cyclic curve is as shown in Figure 3.
Embodiment 3
(1) Li in molar ratio：(Ni+Co+Mn)=1.03:1 by Lithium hydrate and nickel cobalt manganese hydroxide Ni0.7Co0.15Mn0.15(OH)2Mixing, wherein Ni0.7Co0.15Mn0.15(OH)2Quality be 200g, be obtained precursor mixture,
(2) sodium nitrate 2g, ball milling, with roasting in oxygen atmosphere at a temperature of 850 DEG C are added in precursor mixture 20h, obtains nickel cobalt manganese lithiated compound,
(3) crush after cooling down, cross 300 mesh sieves and obtain product LiNi0.7Co0.15Mn0.15O2, its sulfate radical content is 3180ppm.
With resulting material as positive pole, with lithium piece as negative pole, button cell is assembled into, in the voltage model of 3.0～4.3V Interior discharge and recharge is enclosed, the specific capacity of reversible discharge first for measuring the material is 166.4mAh/g, and 50 times circulation conservation rate is 98.7%, Its cyclic curve is as shown in Figure 4.
Comparative example
Comparative example 1
This comparative example is same as Example 3, differs only in and is added without oxidant sodium nitrate.
With resulting material as positive pole, with lithium piece as negative pole, button cell is assembled into, in the voltage model of 3.0～4.3V Interior discharge and recharge is enclosed, the specific capacity of reversible discharge first for measuring the material is 163.1mAh/g, and 50 times circulation conservation rate is 89.5%, Its cyclic curve is as shown in Figure 5.
From Fig. 2～Fig. 5, after adding oxidant, the capacity and cycle performance of resulting materials improves a lot, especially It is that, in terms of cycle performance, as nickel ion is preferably aoxidized in the presence of oxidant, its nickel is reduced with lithium ion mixing, Structure is more stable, therefore the cycle performance of anode material for lithium-ion batteries is greatly improved.
Experimental example
The measure of oxygen purity in 1 laboratory order reaction atmosphere of experimental example
After being -0.08MPa by laboratory scale experiments stove evacuation to negative pressure, purity oxygen is passed through, negative pressure is evacuated to again For -0.08MPa, then purity oxygen is passed through, it is that oxygen purity is reached as high as in 92%, i.e. reaction atmosphere to measure oxygen purity in tail gas To 92%.
The measure of oxygen purity in 2 technical grade reaction atmosphere of experimental example
Purity oxygen is passed through in technical grade experimental furnace, oxygen purity is 86% in measuring tail gas, i.e., is industrially realized anti- Answer oxygen purity in atmosphere be 85% be easily to realize.
The present invention is described in detail above in association with specific embodiment and exemplary example, but these explanations are simultaneously It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention, Various equivalencings, modification can be carried out to technical solution of the present invention and embodiments thereof or is improved, these each fall within the present invention In the range of.Protection scope of the present invention is defined by claims.

Claims (8)

1. a kind of method for preparing the nickelic ternary material of lithium ion cell positive, it is characterised in that the method is comprised the following steps：
(1) it is lithium source by the ratio of mole by lithium source and ternary precursor:Ternary precursor=1:1～1.05:1 mixing, is obtained Precursor mixture, wherein, with the molar amount of elemental lithium in lithium source, the mole of ternary precursor is with three for the mole of lithium source The mole sum meter of all metallic elements in first presoma, the ternary precursor are selected from NixCoyMn1-x-y(OH)2, wherein, 0.6≤x<1,0<y<0.4, and 0<x+y<1；
(2) oxidant being added in obtained precursor mixture in step (1), being ground, raw mixture is obtained, wherein, plus The weight for entering oxidant is the 3～8% of ternary precursor weight, and the oxidant is selected from perchlorate, hypochlorite, permanganic acid Salt, bichromate, nitrate and inorganic peroxide；
(3) raw mixture obtained in step (2) is calcined under oxygen atmosphere, crushes after cooling, sieve, wherein, in oxygen atmosphere Oxygen concentration is 86～92%, and the calcining heat is 700～900 DEG C.
2. method according to claim 1, it is characterised in that lithium source described in step (1) is selected from lithium carbonate, Lithium hydrate And lithium nitrate.
3. method according to claim 1, it is characterised in that ternary precursor is described in step (1) Ni0.9Co0.05Mn0.05(OH)2、Ni0.8Co0.1Mn0.1(OH)2、Ni0.7Co0.15Mn0.15(OH)2、Ni0.6Co0.2Mn0.2(OH)2。
4. method according to claim 1, it is characterised in that oxidant described in step (2) is selected from sodium perchlorate, secondary chlorine Sour sodium, sodium permanganate, sodium dichromate, potassium hyperchlorate, postassium hypochlorite, potassium permanganate, potassium dichromate, magnesium perchlorate, magnesium bichromate, Sodium peroxide, potassium peroxide, Magnesium dioxide and ammonium nitrate.
5. method according to claim 4, it is characterised in that oxidant described in step (2) is selected from sodium perchlorate, secondary chlorine Sour sodium, potassium hyperchlorate, postassium hypochlorite, potassium permanganate, magnesium perchlorate, magnesium bichromate, sodium peroxide, potassium peroxide, Magnesium dioxide And ammonium nitrate.
6. method according to claim 1, it is characterised in that the weight that oxidant is added in step (2) is ternary forerunner The 4～6% of body weight.
7. method according to claim 6, it is characterised in that the weight that oxidant is added in step (2) is ternary forerunner The 5% of body weight.
8. method according to claim 1, it is characterised in that calcining heat is 800 DEG C in step (3).
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