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CN104201378A - 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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Publication number
CN104201378A
CN104201378A CN201410465355.8A CN201410465355A CN104201378A CN 104201378 A CN104201378 A CN 104201378A CN 201410465355 A CN201410465355 A CN 201410465355A CN 104201378 A CN104201378 A CN 104201378A
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lithium
lithium ion
ternary precursor
ion battery
cathode material
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CN104201378B (en
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崔妍
郝振佳
江卫军
文博
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 & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • 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 of preparing the nickelic tertiary cathode material of lithium ion battery
Technical field
The present invention relates to lithium ion anode material preparation field, particularly a kind of method of preparing the nickelic tertiary cathode material of lithium ion battery.
Background technology
Since Sony in 1991 is by lithium ion battery commercialization, lithium ion battery is being brought into play more and more important effect in people's life, and it is widely used in computer now, and camera, on the electronic products such as mobile phone and power vehicle.At present, positive electrode mainly comprises the LiCoO with layer structure 2, LiNiO 2, LiMnO 2, LiNi 1/3co 1/3mn 1/3o 2, LiNi 0.5co 0.2mn 0.3o 2, LiNi 0.8co 0.2o 2, the LiMn of spinel structure 2o 4, LiNi 0.5mn 1.5o 4, the LiFePO of olivine structural 4deng.Along with market improves constantly the requirement of energy density, the lithium ion battery that research and development have high power capacity becomes the task of top priority.
Lithium cobaltate cathode material is synthetic, and easily cycle performance is good, and compacted density is high, is the earliest for one of business-like material, but due to cobalt acid lithium self structure, Li 1-xcoO 2deintercalation coefficient M must meet M≤0.5, otherwise too much lithium deintercalation is caved in positive electrode internal structure, and capacity declines rapidly, cycle performance declines, this structure causes the actual gram volume of cobalt acid lithium only can perform to the half of theoretical gram volume, is 140mAh/g left and right.
Multicomponent material LiNi xco ymn 1-x-yo 2especially to have capacity high for the more much higher first material of nickel content (x>=0.6), circulate good, the advantages such as low price, in the prior art, in anode material for lithium-ion batteries, can make lithium ion battery there is good chemical property as the positive electrode of lithium ion battery with the ternary material that contains nickel cobalt manganese or three kinds of metallic elements of nickel cobalt aluminium, especially, increase with nickel element content wherein, the chemical property increase of lithium ion battery is more remarkable, and therefore, the preparation method of the nickelic ternary material of exploitation preparation is particularly important.
But high-nickel material synthesis condition harshness, Ni when synthetic 2+generation inevitable, its polarizability is less, easily forms high symmetric unordered salt structure, therefore has part Ni 2+be distributed in Li layer, produce lithium ion mixing phenomenon, and the residual alkali of the product surface being synthesized be high, pH is high, and therefore battery process is restive.
Therefore in order to improve its performance, adopt at O 2the method of synthetic material in atmosphere, departs to reduce stoichiometry, improves anodal chemical property; Also can when synthetic material, improve lithium nickel ratio in addition, make lithium ion excessive, reduce the generation of Ar ion mixing occupy-place.Even but still there is the phenomenon of lithium ion mixing significantly in the positive electrode that adopts above-mentioned two kinds of method synthesizeds, cause the irreversible capacity of material to raise, can increase production cost if continue to improve oxygen content.
In prior art, there is the method for preparing the nickelic tertiary cathode material of lithium ion battery under high-load oxygen atmosphere environment by the method for high-temperature calcination, as Chinese patent CN103280575A, a kind of preparation method of lithium ion secondary battery anode material nickle cobalt lithium manganate is disclosed, the method is mixed nickel hydroxide cobalt manganese or hydroxy cobalt nickel oxide manganese powder end by a certain percentage with lithium carbonate powder, again under hot conditions, in oxygen atmosphere, calcine, product after calcining naturally cools to room temperature, after pulverizing, be coated again processing, make required product, the method is in the time preparing positive electrode, need to there is the oxygen atmosphere of high-concentration oxygen, therefore, it is to passing into the purity of oxygen and the sealing of calciner has strict requirement,
But said method all needs the atmosphere of oxygen content more than 90%, and this prepared atmosphere not only needs to pass into high-purity oxygen in reaction system, and the air-tightness of consersion unit is had to strict requirement, although in laboratory, can realize this preparation condition, in industrial production due to Equipment be difficult to realize.
Therefore, need exploitation badly a kind of little to oxygen concentration dependence in prepared atmosphere, and the method for preparing the nickelic positive electrode of lithium ion battery ternary of the nickelic positive electrode excellent performance of lithium ion battery ternary making.
In prior art, for making reaction raw materials be combined to the nickelic tertiary cathode material of lithium ion battery of homogeneous phase, and nickel wherein is farthest existed with trivalent form, conventionally adopt the method for reaction raw materials high-temperature calcination in high-purity oxygen atmosphere, the needed high-purity oxygen atmosphere of the method requires the oxygen passing in experimental furnace to have higher purity on the one hand, at least needs to make the purity of oxygen to reach more than 90%; Require on the other hand experimental furnace to there is good seal, to ensure sneaking into reaction system without other impurity gas in course of reaction, and high-purity oxygen is higher than the manufacturing cost of low-purity oxygen, and strict demand to consersion unit seal, also cause the increase of production cost, therefore, adopt conventional method to prepare the nickelic tertiary cathode material of lithium ion battery, need higher Financial cost.
And the inventor finds after deliberation, some has inorganic oxidizer of strong oxidizing property as perchlorate, hypochlorite, permanganate, bichromate, nitrate and inorganic peroxide etc., they can be in lithium source and ternary precursor course of reaction, under hot conditions, promote the carrying out of synthetic reaction, and can impel the nickel element in ternary precursor to be converted into trivalent by divalence, and can reduce the dependence of raw material to the high oxygen concentration in reaction environment, , can use the oxygen compared with low-purity, be that oxygen purity only needs 85%, therefore, use adds oxidant not only can reduce the cost of oxygen itself in reaction system, and, along with the reduction that experimental furnace seal is required, cost aspect consersion unit also can greatly reduce, therefore, the production cost of preparing the nickelic tertiary cathode material of lithium ion battery after use oxidant significantly reduces.
The experimental furnace using in laboratory, the experimental furnace that the model of producing as Hunan Hua Ye microwave Science and Technology Ltd. is HY-SM1500, carry out vacuumizing for twice after processing in advance, pass into again purity oxygen reaction, recording oxygen purity in tail gas is 92%, and in reaction atmosphere, oxygen purity is 92%, therefore, in can realization response atmosphere in laboratory-scale experimental furnace, oxygen purity reaches 85%, even reaches 90%, and in technical grade is produced, the experimental furnace air-tightness using is far below the experimental furnace using in laboratory, the experimental furnace that the model that Electric Appliance Equipment Co., Ltd as talented in Zhengzhou produces is XD-1200NT, in the time passing into purity oxygen wherein, having large quantity of air sneaks into wherein, recording oxygen purity in tail gas is 86%, in industrial realization response atmosphere oxygen purity reach 90% be difficult to realize, and in reaction atmosphere oxygen purity to reach 85% be easily to realize, therefore, in reaction atmosphere, oxygen purity is reduced to 85% by 90% and has significant industrial applicibility, specifically referring to experimental example 1 and experimental example 2.
In anode material for lithium-ion batteries, some metallic element can not cause negative effect to the performance of anode material for lithium-ion batteries as a small amount of existence of Na element, K element or Mg element, even can promote its performance, and some cations is as NH 4 +deng, it can be decomposed into gas under hot conditions, thus effusion reaction system, and therefore, selective oxidation agent of the present invention is by Na +, K +, Mg 2+with perchlorate, hypochlorite, permanganate or the bichromate of perchlorate, hypochlorite, MnO4 or dichromate ion formation, as sodium perchlorate, clorox, sodium permanganate, sodium dichromate, potassium hyperchlorate, postassium hypochlorite, potassium permanganate, potassium bichromate, magnesium perchlorate or magnesium bichromate; Or be sodium peroxide, potassium peroxide and peromag, or for being at high temperature decomposed into the ammonium nitrate of gas.
In presoma, manganese element exists with+4 valency forms, and Mn 4+/ Mn 7+electrical potential difference be about 1.69eV, and above-mentioned oxidant is therefore, the oxidizability of above-mentioned oxidant is not enough to manganese element by be oxidized to+7 valencys of+4 valencys, it still exists with+4 valencys in the nickelic tertiary cathode material of the lithium ion battery finally making.
Above-mentioned oxidant can both be oxidized to trivalent by the nickel element in presoma by divalence under the condition of preparing the nickelic tertiary cathode material of lithium ion, simultaneously, again can be by manganese element by be oxidized to+7 valencys of+4 valencys, but above-mentioned bichromate is all toxic, and for saving production cost, preferred oxidant of the present invention is sodium perchlorate, clorox, potassium hyperchlorate, postassium hypochlorite, potassium permanganate, magnesium perchlorate or magnesium bichromate, sodium peroxide, potassium peroxide, peromag and ammonium nitrate.
The inventor studies discovery, when add the weight of oxidant be greater than ternary precursor weight 10% time, the consumption of oxidant is excessive, too much oxidant not only increases production cost, though and sodium, potassium or the magnesium elements introduced when a small amount of to the positive electrode making without negative effect, introduction volume too much also can cause the chemical property of positive electrode to decline; And when add the weight of oxidant be less than ternary precursor weight 1% time, oxidant consumption is too small, its oxidation deficiency to reactant, nickel element in presoma can not be completely by+be converted into+3 valencys of divalent, the positive electrode chemical property that causes making promotes not remarkable, therefore, it is 1%～10% of ternary precursor weight that the present invention selects to add the weight of oxidant, be preferably 3～8%, more preferably 4～6%, as 5%.
Step 3, the raw mixture that step 2 is made is calcined under oxygen atmosphere, and cooling rear pulverizing, sieves.
The present invention is more than 85% atmosphere in oxygen concentration, and being preferably oxygen concentration is that in more than 90% atmosphere, calcining can make lithium source react with ternary precursor, and nickel element is wherein oxidized to+3 valencys, makes the nickelic tertiary cathode material of lithium ion battery.
In the time that calcining heat is more than 600 DEG C, reaction is quick, and the nickelic tertiary cathode material of the lithium ion battery making is even, and stable electrochemical property is to save cost, and preferred calcination temperature of the present invention is 600～1000 DEG C, is preferably 700～900 DEG C, as 800 DEG C.
Can, according to the different needs of product, product be crushed to different particle diameters.
Summary of the invention
In order to address the above problem, the inventor has carried out research with keen determination, found that: preparing in the nickelic positive electrode process of lithium ion battery ternary, in reaction system, add a small amount of inorganic oxidizer, can effectively reduce the dependence of reaction system to elevated oxygen level in atmosphere, can in compared with the atmosphere of low oxygen content, can make the nickelic tertiary cathode material of lithium ion battery, and the nickelic tertiary cathode material of the lithium ion battery making has good cycle performance and higher specific capacity, therefore, the present invention is in the time of the nickelic positive electrode of preparation ternary, to introduce oxidant in reaction system, thereby complete the present invention.
The object of the present invention is to provide following aspect:
First aspect, the invention provides the preparation method of the nickelic ternary material of a kind of lithium ion cell positive, it is characterized in that, the method comprises the following steps:
(1) be lithium source with ternary precursor by the ratio of mole by lithium source: ternary precursor=1:1～1.05:1 mixes, make precursor mixture, wherein, the mole in lithium source is in the mole of elemental lithium in lithium source, and the mole of ternary precursor is in the mole sum of all metallic elements in ternary precursor;
(2) in the precursor mixture making in step (1), add oxidant, grind, make raw mixture;
(3) raw mixture step (2) being made is calcined under oxygen atmosphere, and cooling rear pulverizing, sieves.
Second aspect, the present invention also provides said method, it is characterized in that, and described in step (1), lithium source is selected from lithium carbonate, lithium hydroxide and lithium nitrate.
The third aspect, the present invention also provides said method, it is characterized in that, and ternary precursor described in step (1) is nickel cobalt manganese hydroxide or nickel cobalt aluminium hydroxide.
Fourth aspect, the present invention also provides said method, it is characterized in that, and described in step (1), ternary precursor is selected from Ni xco ymn 1-x-y(OH) 2, wherein, 0.6≤x<1,0<y<0.4, and 0<x+y<1, be preferably Ni 0.9co 0.05mn 0.05(OH) 2, Ni 0.8co 0.1mn 0.1(OH) 2, Ni 0.7co 0.15mn 0.15(OH) 2, Ni 0.6co 0.2mn 0.2(OH) 2and Ni 0.8co 0.15al 0.05(OH) 2.
The 5th aspect, the present invention also provides said method, it is characterized in that, and described in step (2), oxidant is selected from perchlorate, hypochlorite, permanganate, bichromate, nitrate and inorganic peroxide.
The 6th aspect, the present invention also provides said method, it is characterized in that, described in step (2), oxidant is selected from sodium perchlorate, clorox, sodium permanganate, sodium dichromate, potassium hyperchlorate, postassium hypochlorite, potassium permanganate, potassium bichromate, magnesium perchlorate, magnesium bichromate, sodium peroxide, potassium peroxide, peromag and ammonium nitrate, is preferably sodium perchlorate, clorox, potassium hyperchlorate, postassium hypochlorite, potassium permanganate, magnesium perchlorate or magnesium bichromate, sodium peroxide, potassium peroxide, peromag and ammonium nitrate.
The 7th aspect, the present invention also provides said method, it is characterized in that, and in step (2), adding the weight of oxidant is 1～10% of ternary precursor weight, is preferably 3～8%, more preferably 4～6%, as 5%.
Eight aspect, the present invention also provides said method, it is characterized in that, and in step (3), in oxygen atmosphere, oxygen concentration is 85～100%, is preferably 90～100%.
The 9th aspect, the present invention also provides said method, it is characterized in that, and in step (3), calcining heat is 600～1000 DEG C, is preferably 700～900 DEG C, as 800 DEG C.
According to method provided by the invention, there is following beneficial effect:
(1) the method is simple to operate, and raw material is easy to obtain;
(2) alleviated the dependence to elevated oxygen level atmosphere while preparing the nickelic tertiary cathode material of lithium ion battery adding of oxidant;
(3) easily realize industrialization, improved production efficiency,
(4) the method has reduced production cost from the aspect such as raw material and production equipment.
Brief description of the drawings
Fig. 1 illustrates the Electronic Speculum figure that makes sample in embodiment 1;
Fig. 2 illustrates the cyclic curve that makes sample in embodiment 1;
Fig. 3 illustrates the cyclic curve that makes sample in embodiment 2;
Fig. 4 illustrates the cyclic curve that makes sample in embodiment 3;
Fig. 5 illustrates the cyclic curve that makes sample in comparative example 1.
Embodiment
Below by the present invention is described in detail, the features and advantages of the invention will become more clear, clear and definite along with these explanations.
The inventor finds through research, in the time of the nickelic tertiary cathode material of preparation, adds oxidant in reaction system, can alleviate the dependence of reactant to rich oxygen content atmosphere in the time of the nickelic tertiary cathode material of preparation, can be efficiently by Ni 2+be converted into Ni 3+, make Ni in lithium ion anode material 3+content significantly increases, thereby has improved the performance using this tertiary cathode material as anodal lithium ion battery.
According to a first aspect of the invention, provide a kind of method of preparing the nickelic tertiary cathode material of lithium ion, the method comprises the following steps:
Step 1, count the mole in lithium source with the mole of elemental lithium in lithium source, count the mole of ternary precursor with the mole sum of all metallic elements in ternary precursor, be lithium source with ternary precursor by the ratio of mole by lithium source: ternary precursor=1:1～1.05:1 mixes, and makes precursor mixture.
The inventor finds after deliberation, work as nickel, cobalt, manganese, the nickel-cobalt-manganese ternary presoma that aluminium and other metallic element are made by homogeneous precipitation method or other method, nickel cobalt aluminium ternary precursor or other ternary precursor, wherein, Determination of multiple metal elements is arranged comparatively rule, mix homogeneous, in the time increasing the content of nickel element, also can make the ternary precursor of homogeneous phase, correspondingly, than using lithium source, nickel source, the nickelic tertiary cathode material that the raw materials such as cobalt source directly make by high-temperature calcination, react the more homogeneous of distribution of various elements in the nickelic tertiary cathode material of the lithium ion making with lithium source with above-mentioned ternary precursor, the arrangement of atom is more regular, and lithium ion battery is just by lithium ion, the deintercalation on positive and negative pole material enters embedding, constantly thereby circulation realizes the recharging effect of lithium ion battery, therefore, the structure of positive electrode is more regular, element distributes and gets over homogeneous, its chemical property is more stable, also be beneficial to and improve its specific capacity and cycle performance, therefore, the present invention selects to prepare the nickelic tertiary cathode material of lithium ion battery using presoma and the lithium source of tertiary cathode material as reaction raw materials.
Due to the nickelic tertiary cathode material stable performance of lithium ion battery that contains nickel, cobalt, three kinds of elements of manganese or contain nickel, cobalt, three kinds of elements of aluminium, and the chemical properties such as specific capacity are good, therefore, the present invention is preferably using nickel cobalt manganese hydroxide or nickel cobalt aluminium hydroxide as the ternary precursor of preparing the nickelic tertiary cathode material of lithium ion.
The present invention is not particularly limited the mol ratio of three kinds of metallic elements in ternary precursor used, and excellent in preferred taking the nickelic tertiary cathode material chemical property of lithium ion that can prepare or make in actual production, being preferably chemical formula is Ni xco ymn 1-x-y(OH) 2ternary precursor, wherein, 0.6≤x<1,0<y<0.4, and 0<x+y<1, as Ni 0.9co 0.05mn 0.05(OH) 2, Ni 0.8co 0.1mn 0.1(OH) 2, Ni 0.7co 0.15mn 0.15(OH) 2, Ni 0.6co 0.2mn 0.2(OH) 2, Ni 0.8co 0.15al 0.05(OH) 2deng.
The present invention is not also particularly limited the source of ternary precursor used, can be for preparing voluntarily, also can be any one commercially available available ternary precursor, the model that nickel cobalt manganese hydroxide, 830 type nickel cobalt aluminium hydroxides and the SUMITOMO CHEMICAL KCC that is 90505 types, 811 types, 622 types as the model of Foshan BOUMPLE circulation Science and Technology Ltd. production produces be the nickel cobalt manganese hydroxide of 701515 types.
The lithium source of selecting in the present invention is the lithium-containing compound that at high temperature can decompose, as lithium carbonate, lithium hydroxide and lithium nitrate etc., these lithium-containing compounds at high temperature can be decomposed into lithium ion and corresponding gas-phase product, wherein, decomposing the lithium ion obtaining reacts with ternary precursor, all the other elements, with gaseous substance, as form effusion reaction systems such as carbon dioxide, water vapour or nitrogen dioxide, finally make the nickelic tertiary cathode material of corresponding lithium ion battery.
In the time that the ratio of the mole of elemental lithium in the nickelic tertiary cathode material of lithium ion battery and the mole sum of other metallic element is 1:1, the chemical property of this positive electrode reaches optimum state, because other metallic element in this positive electrode mainly comes from ternary precursor, therefore, in the time preparing the nickelic tertiary cathode material of lithium ion, the present invention selects the lithium source of comparatively easily acquisition slightly excessive with respect to ternary precursor, , selecting lithium source is lithium source with the ratio of the mole of ternary precursor: nickelic ternary material presoma=1:1～1.05:1, in the time that lithium source is greater than 1.05:1 with the ratio of the mole of ternary precursor, lithium source is excessive in a large number, cause the waste in lithium source, and the chemical property of the nickelic positive electrode of lithium ion battery making also can decrease, in the time that lithium source is less than 1:1 with the ratio of the mole of ternary precursor, lithium source quantity not sufficient, in the nickelic positive electrode of lithium ion battery making, lack enough lithiums in positive and negative storeroom deintercalation and enter embedding, cause its chemical property to reduce, wherein, the mole in lithium source is in the mole of elemental lithium in lithium source, and the mole of nickelic ternary material presoma is in the mole sum of all metallic elements in nickelic ternary material presoma.
Step 2 adds oxidant in the precursor mixture making in step 1, grinds, and makes raw mixture.
Embodiment
In the present embodiment and comparative example, experimental furnace used is technical grade experimental furnace, the experimental furnace that the model of producing for the talented Electric Appliance Equipment Co., Ltd in Zhengzhou is XD-1200NT;
Ternary precursor Ni used 0.8co 0.1mn 0.1(OH) 2the ternary precursor that the model of producing for Foshan BOUMPLE circulation Science and Technology Ltd. is 811;
Ternary precursor Ni used 0.8co 0.15al 0.05(OH) 2the ternary precursor that the model of producing for Foshan BOUMPLE circulation Science and Technology Ltd. is 830;
Ternary precursor Ni used 0.7co 0.15mn 0.15(OH) 2the ternary precursor that the model of producing for SUMITOMO CHEMICAL KCC is 701515.
In experimental example, technical grade experimental furnace used is the experimental furnace that the model that the talented Electric Appliance Equipment Co., Ltd in Zhengzhou produces is XD-1200NT; Laboratory-scale experimental furnace used is the experimental furnace that the model of Hunan Hua Ye microwave Science and Technology Ltd. production is HY-SM1500.
embodiment 1
(1) Li:(Ni+Co+Mn in molar ratio)=1.02:1 is lithium hydroxide and nickel cobalt manganese hydroxide Ni 0.8co 0.1mn 0.1(OH) 2mix wherein Ni 0.8co 0.1mn 0.1(OH) 2quality be 100g, make precursor mixture,
(2) in precursor mixture, add potassium permanganate 5g, ball milling, at the temperature of 780 DEG C in oxygen atmosphere roasting 20h, obtain nickel cobalt manganese lithiated compound,
(3), by the cooling rear pulverizing of nickel cobalt manganese lithiated compound, cross 300 mesh sieves and obtain product LiNi 0.8co 0.1mn 0.1o 2, its sulfate radical content is 2800ppm, the D50 of granularity is 10.6 μ m.
Taking the material that obtained as anodal, taking lithium sheet as negative pole, be assembled into button cell, in the voltage range of 3.0～4.3V, discharge and recharge, the reversible specific discharge capacity first that records this material is 172.3mAh/g, 50 times circulation conservation rate is 97.5%, and as shown in Figure 1, cyclic curve as shown in Figure 2 for its scanning electron microscope (SEM) photograph.
embodiment 2
(1) Li:(Ni+Co+Al in molar ratio)=1.01:1 is lithium hydroxide and nickel cobalt manganese hydroxide Ni 0.8co 0.15al 0.05(OH) 2mix wherein Ni 0.8co 0.15al 0.05(OH) 2quality be 200g, make precursor mixture,
(2) in precursor mixture, add ammonium nitrate 10g, ball milling, at the temperature of 800 DEG C with oxygen atmosphere in roasting 20h, obtain nickel cobalt aluminium lithiated compound,
(3) cooling rear pulverizing, crosses 300 mesh sieves and obtains product LiNi 0.8co 0.15al 0.05o 2, its sulfate radical content is 2660ppm.
Taking the material that obtained as anodal, taking lithium sheet as negative pole, be assembled into button cell, in the voltage range of 3.0～4.3V, discharge and recharge, the reversible specific discharge capacity first that records this material is 173.3mAh/g, and 50 times circulation conservation rate is 97.1%, and its cyclic curve as shown in Figure 3.
embodiment 3
(1) Li:(Ni+Co+Mn in molar ratio)=1.03:1 is lithium hydroxide and nickel cobalt manganese hydroxide Ni 0.7co 0.15mn 0.15(OH) 2mix wherein Ni 0.7co 0.15mn 0.15(OH) 2quality be 200g, make precursor mixture,
(2) in precursor mixture, add sodium nitrate 2g, ball milling, at the temperature of 850 DEG C with oxygen atmosphere in roasting 20h, obtain nickel cobalt manganese lithiated compound,
(3) cooling rear pulverizing, crosses 300 mesh sieves and obtains product LiNi 0.7co 0.15mn 0.15o 2, its sulfate radical content is 3180ppm.
Taking the material that obtained as anodal, taking lithium sheet as negative pole, be assembled into button cell, in the voltage range of 3.0～4.3V, discharge and recharge, the reversible specific discharge capacity first that records this material is 166.4mAh/g, and 50 times circulation conservation rate is 98.7%, and its cyclic curve as shown in Figure 4.
Comparative example
comparative example 1
This comparative example is identical with embodiment 3, and difference is only not add oxidant sodium nitrate.
Taking the material that obtained as anodal, taking lithium sheet as negative pole, be assembled into button cell, in the voltage range of 3.0～4.3V, discharge and recharge, the reversible specific discharge capacity first that records this material is 163.1mAh/g, and 50 times circulation conservation rate is 89.5%, and its cyclic curve as shown in Figure 5.
From Fig. 2～Fig. 5, add capacity and the cycle performance of resulting materials after oxidant to improve a lot, especially aspect cycle performance, because nickel ion is better oxidized under the effect of oxidant, its nickel and lithium ion mixing reduce, structure is more stable, and therefore the cycle performance of anode material for lithium-ion batteries is greatly improved.
Experimental example
the mensuration of oxygen purity in experimental example 1 laboratory-scale reaction atmosphere
Laboratory-scale experimental furnace is evacuated to negative pressure for after-0.08MPa, passes into purity oxygen, be again evacuated to negative pressure for-0.08MPa, then pass into purity oxygen, recording oxygen purity in tail gas is 92%, and in reaction atmosphere, oxygen purity can reach 92%.
the mensuration of oxygen purity in experimental example 2 technical grade reaction atmospheres
In technical grade experimental furnace, pass into purity oxygen, recording oxygen purity in tail gas is 86%, and in industrial realization response atmosphere, oxygen purity is 85% to be easily to realize.
In conjunction with embodiment and exemplary example, the present invention is had been described in detail above, but these explanations can not be interpreted as limitation of the present invention.It will be appreciated by those skilled in the art that in the situation that not departing from spirit and scope of the invention, can carry out multiple replacement of equal value, modify or improve technical solution of the present invention and execution mode thereof, these all fall within the scope of the present invention.Protection scope of the present invention is as the criterion with claims.

Claims (9)

1. a method of preparing the nickelic ternary material of lithium ion cell positive, is characterized in that, the method comprises the following steps:
(1) be lithium source with ternary precursor by the ratio of mole by lithium source: ternary precursor=1:1～1.05:1 mixes, make precursor mixture, wherein, the mole in lithium source is in the mole of elemental lithium in lithium source, and the mole of ternary precursor is in the mole sum of all metallic elements in ternary precursor;
(2) in the precursor mixture making in step (1), add oxidant, grind, make raw mixture;
(3) raw mixture step (2) being made is calcined under oxygen atmosphere, and cooling rear pulverizing, sieves.
2. method according to claim 1, is characterized in that, described in step (1), lithium source is selected from lithium carbonate, lithium hydroxide and lithium nitrate.
3. method according to claim 1, is characterized in that, ternary precursor described in step (1) is nickel cobalt manganese hydroxide or nickel cobalt aluminium hydroxide.
4. method according to claim 1, is characterized in that, described in step (1), ternary precursor is selected from Ni xco ymn 1-x-y(OH) 2, wherein, 0.6≤x<1,0<y<0.4, and 0<x+y<1, be preferably Ni 0.9co 0.05mn 0.05(OH) 2, Ni 0.8co 0.1mn 0.1(OH) 2, Ni 0.7co 0.15mn 0.15(OH) 2, Ni 0.6co 0.2mn 0.2(OH) 2and Ni 0.8co 0.15al 0.05(OH) 2.
5. method according to claim 1, is characterized in that, described in step (2), oxidant is selected from perchlorate, hypochlorite, permanganate, bichromate, nitrate and inorganic peroxide.
6. method according to claim 1, it is characterized in that, described in step (2), oxidant is selected from sodium perchlorate, clorox, sodium permanganate, sodium dichromate, potassium hyperchlorate, postassium hypochlorite, potassium permanganate, potassium bichromate, magnesium perchlorate, magnesium bichromate, sodium peroxide, potassium peroxide, peromag and ammonium nitrate, is preferably sodium perchlorate, clorox, potassium hyperchlorate, postassium hypochlorite, potassium permanganate, magnesium perchlorate or magnesium bichromate, sodium peroxide, potassium peroxide, peromag and ammonium nitrate.
7. method according to claim 1, is characterized in that, in step (2), adding the weight of oxidant is 1～10% of ternary precursor weight, is preferably 3～8%, more preferably 4～6%, and as 5%.
8. method according to claim 1, is characterized in that, in step (3), in oxygen atmosphere, oxygen concentration is 85～100%, is preferably 90～100%.
9. method according to claim 1, is characterized in that, in step (3), calcining heat is 600～1000 DEG C, is preferably 700～900 DEG C, as 800 DEG C.
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