CN109638251A - A kind of preparation method of the modified nickelic positive electrode of gradient sintering gas phase Fluorin doped - Google Patents

A kind of preparation method of the modified nickelic positive electrode of gradient sintering gas phase Fluorin doped Download PDF

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CN109638251A
CN109638251A CN201811521420.9A CN201811521420A CN109638251A CN 109638251 A CN109638251 A CN 109638251A CN 201811521420 A CN201811521420 A CN 201811521420A CN 109638251 A CN109638251 A CN 109638251A
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positive electrode
gas phase
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fluorin doped
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CN109638251B (en
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钱飞鹏
马岩华
唐朝辉
赵春阳
李佳军
邓亚烽
陆科炯
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Wuxi Spar New Energy Ltd By Share Ltd
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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    • H—ELECTRICITY
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    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a kind of preparation methods of the modified nickelic positive electrode of gradient sintering gas phase Fluorin doped, comprising the following steps: 1) is sufficiently mixed lithium source uniformly with nickelic；2) it, is placed in atmosphere furnace first quick heating rate and rises to 480~530 DEG C, then heating rate rises to 700-800 DEG C of heat preservation 8-15h at a slow speed, and is continually fed into high purity oxygen gas, keeps micro-positive pressure in furnace；3), then cooling rate is down to 550-650 DEG C of heat preservation 4-8h, and closes high purity oxygen gas, is passed through high-purity fluorine gas, keeps micro-positive pressure in stream furnace；4), naturally cold and close air inlet and exhaust outlet, make to circulate in furnace without atmosphere；5), target product is obtained after taking-up processing.Surface doping uniformity and consistency of the present invention are more preferable；Using gradient sintering technology, high-nickel material Ni during the sintering process ensure that2+It can be substantially oxidized as Ni3+, improve the specific capacity and cycle performance of material.

Description

A kind of preparation method of the modified nickelic positive electrode of gradient sintering gas phase Fluorin doped
Technical field
The invention belongs to anode material for lithium-ion batteries technical fields, and it is modified to be related to a kind of gradient sintering surface vapor Fluorin doped The preparation method of nickelic positive electrode.
Background technique
The anode material for lithium-ion batteries of existing market mainstream mainly has cobalt acid lithium (LiCoO2), LiMn2O4 (LiMn2O4)、 LiFePO4 (LiFePO4), ternary material (nickle cobalt lithium manganate and nickel cobalt lithium aluminate).Cobalt acid lithium (LiCoO2) due to cobalt resource It is rare, its development potentiality of expensive price limit；LiMn2O4 (LiMn2O4Although) low in cost, resourceful, its energy The disadvantages of metric density is lower, and high temperature cyclic performance is poor also limits its large-scale application；LiFePO4 (LiFePO4Although) tool The advantages that standby good structural stability and extensive, cheap cyclicity, raw material sources, but due to its electronic conductivity compared with It is low, and the factors such as the diffusion rate of lithium ion inside it is smaller, and energy density is relatively low also limit to a certain extent its Multi-field development.Ternary material (nickle cobalt lithium manganate and nickel cobalt lithium aluminate) is high by its energy density, and cycle performance is excellent etc. Advantage, the market share have occupied positive electrode leading position.
The ternary material of nickelic series (80% or more nickel molar content) has the advantages such as capacity is high, price is low, is current The important development direction of tertiary cathode material.The main stream approach for synthesizing the ternary material of nickelic series at present is high temperature solid-state method, It is aided with high concentration oxygen atmosphere and is sintered synthesis final products.But nickelic ternary material synthesis process is an oxidation reaction, It needs Ni2+It is oxidizing to Ni3+, and reacting is reversible reaction, therefore conventional pure oxygen atmosphere is difficult completely the Ni in material2+ It is oxidizing to Ni3+, cause material structure imperfect in this way, lithium nickel mixing is serious, and the residual lithium of material surface is higher, and finished-product material Spontaneous reaction, Ni can occur for grain surface3+It is changed into Ni2+, discharge O2-, so as to cause material capacity reduction, cycle performance decline etc. Negative consequence.
Summary of the invention
The technical problem to be solved by the present invention is to overcome nickelic ternary materials in the prior art, and lithium nickel mixing is serious, material Expect that the residual lithium in surface is higher, so as to cause material capacity reduction, the defect of cycle performance decline provides a kind of gradient sintering surface gas The preparation method of the modified nickelic positive electrode of phase Fluorin doped.
In order to solve the above-mentioned technical problems, the present invention provides the following technical solutions:
A kind of preparation method of the modified nickelic positive electrode of gradient sintering gas phase Fluorin doped, comprising the following steps:
1) it by lithium source and nickelic presoma, is placed in high-speed mixer and is sufficiently mixed uniformly；
2), 1) material being uniformly mixed in is placed in atmosphere furnace and rises to 480~530 with the heating rate of 3~7 DEG C/min DEG C, then 700-800 DEG C of heat preservation 8-15h is risen to the heating rate of 0.6~1.5 DEG C/min, and heat up again and insulating process in lead to Enter high purity oxygen gas, flow 5-15L/min keeps micro-positive pressure in furnace；
3) 550-650 DEG C of heat preservation 4-8h then, is down to the cooling rate of 2~5 DEG C/min, is closed in cooling and insulating process High purity oxygen gas is closed, is passed through high-purity fluorine gas, flow 5-15L/min, furnace is interior to keep micro-positive pressure；
4) 90~110 DEG C, are naturally cooled to, air inlet and exhaust outlet are closed in temperature-fall period, makes to circulate in furnace without atmosphere；
5) material is crushed after, taking out cooling, is sieved, is obtained target product.
Preferably, lithium source and the molar ratio of nickelic presoma are 1~1.05:1 in the step 1).
Further, lithium source is LITHIUM BATTERY LiOH in the step 1), and granularity D50 is 6-10 μm, and nickelic presoma is nickel Based hybroxide, it is 9-13 μm that the molar ratio of nickel, which is 80% or more, D50,.
Further, 500 DEG C are risen to the heating rate of 5 DEG C/min in the step 2), then with the heating speed of 1 DEG C/min Degree rises to 700-800 DEG C of heat preservation 8-15h.
Further, 550-650 DEG C of heat preservation 4-8h is down to the cooling rate of 3 DEG C/min in the step 3).
Further, the equal > 99% of the purity of the high purity oxygen gas in the step 2) and the high-purity fluorine gas in step 3).
Further, the step 2) and micro-positive pressure in furnace in step 3) are 0.1-1.0Kpa.
Further, 100 DEG C are cooled in the step 4).
Further, the inner cavity size of the atmosphere furnace is 30L.
The beneficial effects obtained by the present invention are as follows being:
1) since Fluorin doped mode is gas phase doping, material comes into full contact with fluorine gas during the sintering process, and surface doping is equal Even property and consistency are more preferable；
2), due to using gradient sintering technology, it ensure that atmosphere is dense when oxygen atmosphere heat preservation platform keeps the temperature platform with fluorine atmosphere Degree can ensure that high-nickel material Ni during the sintering process to 95% or more2+It can be substantially oxidized as Ni3+, make high-nickel material Structure is more complete, and the mixing of lithium nickel has also obtained good inhibition, and the residual lithium in the surface of material has also obtained good control, improves The specific capacity and cycle performance of material；
3), the stability of the covalent bond F-M formed due to material surface fluorine doped, fluorine and metal is better than what oxygen was formed with metal Covalent bond O-M, doping F element replace part oxygen element to inhibit reacting from granting oxygen for high-nickel material surface well, stablize The crystal structure of high-nickel material makes the cyclicity of high-nickel material and stability be improved.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the circulation figure of the embodiment of the present invention 1 and comparative example 1；
Fig. 2 is the circulation figure of embodiment 2 and comparative example 2.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used In the description and interpretation present invention, it is not intended to limit the present invention.
Embodiment 1
1) it is 462.5g that, 1.03:1, which weighs D50=6.5 μm of LITHIUM BATTERY LiOH weight, in molar ratio, and D50=9.6 μm nickelic Presoma (Ni0.835Co0.115Mn0.05)(OH)2Weight is 1000g, is placed in high efficient mixer, mixed with the revolving speed of 1000r/min It discharges after closing 25 minutes；
2) the mixture 1000g in step 1, is taken to rise to 500 DEG C in being placed in atmosphere furnace with the heating rate of 5 DEG C/min, 770 DEG C of heat preservation 12h are risen to the heating rate of 1 DEG C/min again, are passed through high purity oxygen gas in this heating and insulating process, flow is 5L/min, furnace is interior to keep micro-positive pressure, pressure 0.1Kpa；
3) 650 DEG C of heat preservation 6h, are down to the cooling rate of 3 DEG C/min, close high purity oxygen gas in this cooling and insulating process, It is passed through high-purity fluorine gas, flow 5L/min, furnace is interior to keep micro-positive pressure, pressure 0.1Kpa；
4) 100 DEG C, are naturally cooled to, air inlet and exhaust outlet are closed in this temperature-fall period, makes to circulate in furnace without atmosphere；
5) material is crushed after, taking out cooling, is sieved, is obtained product.
Comparative example 1
1) it is 462.5g that, 1.03:1, which weighs D50=6.5 μm of LITHIUM BATTERY LiOH weight, in molar ratio, and D50=9.6 μm nickelic Presoma (Ni0.835Co0.115Mn0.05)(OH)2Weight is 1000g, is placed in high efficient mixer, mixed with the revolving speed of 1000r/min It discharges after closing 25 minutes；
2) the mixture 1000g in step 1, is taken to rise to 500 DEG C in being placed in atmosphere furnace with the heating rate of 5 DEG C/min, 770 DEG C of heat preservation 12h are risen to the heating rate of 1 DEG C/min again, are passed through high purity oxygen gas in this heating and insulating process, flow is 5L/min, furnace is interior to keep micro-positive pressure, pressure 0.1Kpa；
3) 650 DEG C of heat preservation 6h then, are down to the cooling rate of 3 DEG C/min, this cooling and insulating process are passed through high pure oxygen Gas, flow 5L/min, furnace is interior to keep micro-positive pressure, pressure 0.1Kpa；
4) 100 DEG C, are naturally cooled to, air inlet and exhaust outlet are closed in this temperature-fall period, makes to circulate in furnace without atmosphere；
5) material is crushed after taking out cooling, is sieved, is obtained product.
Embodiment 2:
1) it is 445.8g that, 1.02:1, which weighs D50=8.2 μm of LITHIUM BATTERY LiOH weight, in molar ratio, and D50=12.5 μm nickelic Presoma (Ni0.88Co0.09Al0.03)(OH)2Weight is 1000g, is placed in high efficient mixer, is mixed with the revolving speed of 1000r/min It discharges after 25 minutes；
2) the mixture 1000g in step 1, is taken to rise to 500 DEG C in being placed in atmosphere furnace with the heating rate of 5 DEG C/min, 750 DEG C of heat preservation 10h are risen to the heating rate of 1 DEG C/min again, are passed through high purity oxygen gas in this heating and insulating process, flow is 15L/min, furnace is interior to keep micro-positive pressure, pressure 0.5Kpa；
3) 550 DEG C of heat preservation 6h, are down to the cooling rate of 3 DEG C/min, close high purity oxygen gas in this cooling and insulating process, It is passed through high-purity fluorine gas, flow 15L/min, furnace is interior to keep micro-positive pressure, pressure 0.5Kpa；
4) 100 DEG C, are naturally cooled to, air inlet and exhaust outlet are closed in this temperature-fall period, makes to circulate in furnace without atmosphere；
5) material is crushed after, taking out cooling, is sieved, is obtained product.
Comparative example 2:
1) it is 445.8g that, 1.02:1, which weighs D50=8.2 μm of LITHIUM BATTERY LiOH weight, in molar ratio, and D50=12.5 μm nickelic Presoma (Ni0.88Co0.09Al0.03)(OH)2Weight is 1000g, is placed in high efficient mixer, is mixed with the revolving speed of 1000r/min It discharges after 25 minutes；
2) the mixture 1000g in step 1, is taken to rise to 500 DEG C in being placed in atmosphere furnace with the heating rate of 5 DEG C/min, 750 DEG C of heat preservation 10h are risen to the heating rate of 1 DEG C/min again, are passed through high purity oxygen gas in this heating and insulating process, flow is 15L/min, furnace is interior to keep micro-positive pressure, pressure 0.5Kpa；
3) 550 DEG C of heat preservation 6h, are down to the cooling rate of 3 DEG C/min, are passed through high purity oxygen gas in this cooling and insulating process, Flow is 15L/min, keeps micro-positive pressure, pressure 0.5Kpa in furnace；
4) 100 DEG C, are naturally cooled to, air inlet and exhaust outlet are closed in this temperature-fall period, makes to circulate in furnace without atmosphere；
5) material is crushed after, taking out cooling, is sieved, is obtained product.
Test result:
1. the product of Example 1, embodiment 2 and comparative example 1, comparative example 2 is EDS test, analytical element F and O respectively Content, the results are shown in Table 1:
1 EDS test result of table
As can be seen from Table 1, there is F element in embodiment 1 and embodiment 2, without F element in comparative example 1 and comparative example 2.
2. the product of Example 1, embodiment 2 and comparative example 1, comparative example 2 does the residual lithium test in surface respectively, LiOH is analyzed And Li2CO3 content, the results are shown in Table 2:
Table 2: the residual lithium test result in surface
Sample/residual lithium LiOH% Li2CO3% Total Li%
Embodiment 1 0.2961 0.2610 0.1349
Comparative example 1 0.4916 0.4119 0.2199
Embodiment 2 0.4182 0.1456 0.1486
Comparative example 2 0.5224 0.3766 0.2226
3. the product of Example 1, embodiment 2 and comparative example 1, comparative example 2 does full battery test, test voltage model respectively It encloses for 2.75V-4.2V, multiplying power is 1C charge and discharge, is recycled 50 weeks respectively.Capacity retention ratio 94.5% after embodiment 1 recycles 50 weeks, it is right Ratio 1 recycles 50 weeks capacity retention ratios 80.6%, and embodiment 2 recycles 50 weeks capacity retention ratios 95.3%, and comparative example 2 recycles 50 weeks Conservation rate 85.2% illustrates the modified cycle performance for improving material of F element doping.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention, Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features. All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention Within protection scope.

Claims (9)

1. a kind of preparation method of the modified nickelic positive electrode of gradient sintering gas phase Fluorin doped, which is characterized in that including following step It is rapid:
1) it by lithium source and nickelic presoma, is placed in high-speed mixer and is sufficiently mixed uniformly；
2), 1) material being uniformly mixed in is placed in atmosphere furnace and rises to 480~530 DEG C with the heating rate of 3~7 DEG C/min, then Rise to 700-800 DEG C of heat preservation 8-15h with the heating rate of 0.6~1.5 DEG C/min, and heat up again and insulating process in be passed through it is high-purity Oxygen, flow 5-15L/min keep micro-positive pressure in furnace；
3) 550-650 DEG C of heat preservation 4-8h then, is down to the cooling rate of 2~5 DEG C/min, is closed in cooling and insulating process high Purity oxygen is passed through high-purity fluorine gas, and flow 5-15L/min, furnace is interior to keep micro-positive pressure；
4) 90~110 DEG C, are naturally cooled to, air inlet and exhaust outlet are closed in temperature-fall period, makes to circulate in furnace without atmosphere；
5) material is crushed after, taking out cooling, is sieved, is obtained target product.
2. the preparation method of the modified nickelic positive electrode of gradient sintering gas phase Fluorin doped as described in claim 1, feature exist In lithium source and the molar ratio of nickelic presoma are 1~1.05:1 in the step 1).
3. the preparation method of the modified nickelic positive electrode of gradient sintering gas phase Fluorin doped as claimed in claim 2, feature exist In lithium source is LITHIUM BATTERY LiOH in the step 1), and granularity D50 is 6-10 μm, and nickelic presoma is Ni-based hydroxide, nickel Molar ratio is that 80% or more, D50 is 9-13 μm.
4. the preparation method of the modified nickelic positive electrode of gradient sintering gas phase Fluorin doped as described in claim 1, feature exist In rising to 500 DEG C in the step 2) with the heating rate of 5 DEG C/min, then rise to 700-800 with the heating rate of 1 DEG C/min DEG C heat preservation 8-15h.
5. the preparation method of the modified nickelic positive electrode of gradient sintering gas phase Fluorin doped as described in claim 1, feature exist In being down to 550-650 DEG C of heat preservation 4-8h in the step 3) with the cooling rate of 3 DEG C/min.
6. the preparation method of the modified nickelic positive electrode of gradient sintering gas phase Fluorin doped as described in claim 1, feature exist In the equal > 99% of purity of the high-purity fluorine gas in high purity oxygen gas and step 3) in the step 2).
7. the preparation method of the modified nickelic positive electrode of gradient sintering gas phase Fluorin doped as claimed in claim 6, feature exist In micro-positive pressure is 0.1-1.0Kpa in furnace in the step 2) and step 3).
8. the preparation method of the modified nickelic positive electrode of gradient sintering gas phase Fluorin doped as described in claim 1, feature exist In being cooled to 100 DEG C in the step 4).
9. the preparation method of the modified nickelic positive electrode of gradient sintering gas phase Fluorin doped as described in claim 1, feature exist In the inner cavity size of the atmosphere furnace is 30L.
CN201811521420.9A 2018-12-12 2018-12-12 Preparation method of gradient sintered gas-phase fluorine-doped modified high-nickel cathode material Active CN109638251B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1816926A (en) * 2003-08-19 2006-08-09 清美化学股份有限公司 Positive electrode material for lithium secondary cell and process for producing the same
CN105470497A (en) * 2015-11-26 2016-04-06 中信大锰矿业有限责任公司大新锰矿分公司 Preparation method of fluorine ion-doped lithium nickel manganese oxide
CN106602015A (en) * 2016-12-21 2017-04-26 湖北金泉新材料有限责任公司 Preparation method for fluorine-doped nickel-cobalt-manganese system ternary positive electrode material and prepared material
CN107195863A (en) * 2017-06-07 2017-09-22 四川科能锂电有限公司 The preparation method of nickel-cobalt-manganternary ternary anode material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1816926A (en) * 2003-08-19 2006-08-09 清美化学股份有限公司 Positive electrode material for lithium secondary cell and process for producing the same
CN105470497A (en) * 2015-11-26 2016-04-06 中信大锰矿业有限责任公司大新锰矿分公司 Preparation method of fluorine ion-doped lithium nickel manganese oxide
CN106602015A (en) * 2016-12-21 2017-04-26 湖北金泉新材料有限责任公司 Preparation method for fluorine-doped nickel-cobalt-manganese system ternary positive electrode material and prepared material
CN107195863A (en) * 2017-06-07 2017-09-22 四川科能锂电有限公司 The preparation method of nickel-cobalt-manganternary ternary anode material

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