CN101106190A - A low thermal solid phase method for coating the surface of lithium ion cathode material - Google Patents

A low thermal solid phase method for coating the surface of lithium ion cathode material Download PDF

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CN101106190A
CN101106190A CNA2007100355719A CN200710035571A CN101106190A CN 101106190 A CN101106190 A CN 101106190A CN A2007100355719 A CNA2007100355719 A CN A2007100355719A CN 200710035571 A CN200710035571 A CN 200710035571A CN 101106190 A CN101106190 A CN 101106190A
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lithium ion
anode material
ion anode
solid phase
low thermal
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CN100470889C (en
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胡国荣
邓新荣
彭忠东
杜柯
李劼
刘业翔
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Central South University
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Central South University
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Abstract

The invention relates to a low heating solid state reaction method for the surface coating of lithium-ion positive material. The lithium-ion positive material, the metal salt for coating and the solid state powder for low heating solid state reaction are mixed with the molar ratio of 1: (0.001-0.3): (0.001 -0.3) and mixed uniformly by ball milling, and the mixture is obtained; then, the mixture is cleaned by deionized water and dried at 50 -120 DEG C, and the coated lithium-ion positive material is obtained; the cleaned and dried lithium-ion positive material is roasted again at 400 -850 DEG C for 0.5-6 hrs to obtain the coated lithium-ion positive material. The invention is simple in technique, easy to operate, and environmental-friendly. The coated lithium-ion positive material has the improved electrochemical properties and safety performance, applied to industrial production.

Description

A kind of lithium ion anode material is carried out surface coated low thermal solid phase method
Technical field
The invention belongs to a kind of anode material for lithium-ion batteries preparing technical field, related to and a kind of lithium ion anode material has been carried out surface coated low thermal solid phase method.
Background technology
Lithium ion battery is as a kind of new generation of green secondary cell, have that volume is little, in light weight, capacity is big, self discharge is little, have extended cycle life, advantage such as memory-less effect, one of it not only can be used for fields such as portable electronics, artificial satellite, Aero-Space, or the back-up source of electric automobile.As the desirable energy of 21 century, lithium ion battery has caused global attention.And as the critical material of lithium ion battery development, lithium ion anode material just more seems important.
In recent years, the various countries researcher once attempted in the different disposal mode positive electrode being carried out bulk phase-doped and surface coating modification, and wherein the mode of improving positive electrode with surface treatment especially just is being subjected to attention more and more widely.The method is to use nonconducting metal oxide or other positive electrode, is coated on all kinds of positive electrodes surface, to reach the purpose of improving electrochemical properties.Positive electrode through after the coating of surface can improve the cyclical stability of material and promote its operating voltage, and bearing high-tension ability even also has remarkable lifting.
The method of coated lithium ion positive electrode mainly contains at present: sol-gel process, the non-homogeneous precipitation method, mechanical fusion method etc.
Sol-gel process is on the surface coated lithium ion anode material of need surface metal alkoxide or inorganic salts directly to be formed colloidal sol or form colloidal sol with fixed attention through separating through hydrolysis, makes the solute polymeric gelization then, and again with gel drying, sintering obtains powder body material at last.This method can be carried out under temperate condition, and the powder specific surface that obtains is big, and chemical uniformity is good, but shrinks when dry greatly, and the gained powder sintering is bad, and the reaction time is longer, needs a few days just can finish, and is difficult to reach industrialization demands.Metal alkoxide costs an arm and a leg in addition, and the solvent of alkoxide is poisonous usually.
The non-homogeneous precipitation method are prevailing methods of liquid-phase chemical reaction surface coated lithium ion positive electrode.Its principle is: in the solution of soluble-salt that comprises one or more ions and the surface coated positive electrode of need, after adding precipitation reagent, or under uniform temperature, make solution generation hydrolysis, making its surface at positive electrode form insoluble hydroxide, hydrous oxide or salt separates out from solution, and solvent closed original anion flush away in the solution, promptly obtaining required oxide powder through thermal decomposition or dehydration.The characteristics of this method maximum are exactly: the solution nucleation is fast, and is easy to control, and equipment is simple, can make highly purified product.But sad filter is easily reunited and water consumption, and environmental pollution is big.
In article of delivering and patent, do not see at present the report that adopts with same materials of the present invention and synthetic this material of method as yet.
The content of invention
The object of the present invention is to provide and a kind of lithium ion anode material is carried out surface coated low thermal solid phase method, solved complex process and weakness more rambunctious in traditional positive electrode surface coating process.
The objective of the invention is to realize by following manner;
A kind of lithium ion anode material is carried out surface coated low thermal solid phase method, may further comprise the steps:
A: with lithium ion anode material, as slaine that coats usefulness and the pressed powder that can carry out low fever solid phase reaction with it, by 1: (0.001-0.3): (0.001-0.3) mixed in molar ratio, ball milling make its even mixing, get mixture;
B: use the deionized water wash said mixture, the lithium ion anode material that obtains coating in 50-120 ℃ of oven dry;
C: the lithium that the lithium ion anode material after the above-mentioned oven dry was obtained coating in 400-850 ℃ of roasting 0.5-6 hour again is from the positive electrode product.
Can be selected from a kind of in Si, Mg, Al, Ti, Ni, Mn, Co, Ce, Y, the Fe slaine etc. or several combination under compatible situation as the material that coats usefulness, its fusing point of described slaine must be lower than 300 ℃;
Described pressed powder is selected from LiOHH 2O, NaOH, Na 2CO 3, NH 4A kind of among the Cl or several combination under compatible situation.
A kind of in Mg, Al, Ti, Ni, Mn, Co, Ce, Y, the Fe slaine etc. or under compatible situation several combination energy and LiOHH 2O, NaOH, Na 2CO 3, Na 3PO 4Deng in a kind of or under compatible situation several combinations react; Slaine energy and the NH of Si 4The Cl reaction.
Lithium ion anode material is LiCoO 2, LiMn 2O 4, LiFePO 4, LiNi 1/3Mn 1/3Co 1/3O 2, LiNi 1-xCo xO 2(x＜1) or LiNi 1-xM xO 2(M is a doping metals, x＜1).
Coating is by the 0.1-5wt% of coated lithium ion positive electrode, by percentage to the quality.
Do not need solvent in the course of reaction of the present invention, possess the reaction condition gentleness, be easy to control, process route is short, and raw material is inexpensive and be easy to obtain advantages of environment protection.Many shortcomings such as it is big to have overcome in the conventional surface method for coating wastewater discharge, and the reaction time is long.The chemical property and the security performance of the lithium ion anode material after the coating are greatly improved, and are suitable for suitability for industrialized production.
Description of drawings:
Fig. 1 does not coat and coats Al 2O 3LiCoO 2(a does not coat Al to the lithium ion anode material sem photograph 2O 3LiCoO 2B coats Al 2O 3LiCoO 2).
Fig. 2 does not coat and coats Al 2O 3LiCoO 2(a does not coat Al to the cycle performance figure of lithium ion anode material 2O 3LiCoO 2B coats Al 2O 3LiCoO 2).
Fig. 3 does not coat and coats Co 3(PO 4) 2LiMn 2O 4(a does not coat Co to the cycle performance figure of lithium ion anode material 3(PO 4) 2LiMn 2O 4B coats Co 3(PO 4) 2LiMn 2O 4).
Fig. 4 does not coat and coats AlPO 4LiNi 0.8Co 0.2O 2(a does not coat AlPO to the cycle performance figure of lithium ion anode material 4LiNi 0.8Co 0.2O 2B coats AlPO 4LiNi 0.8Co 0.2O 2).
Fig. 5 does not coat and coated Si O 2LiNi 1/3Mn 1/3Co 1/3O 2The sem photograph of lithium ion anode material (a, not coated Si O 2LiNi 1/3Mn 1/3Co 1/3O 2B, coated Si O 2LiNi 1/3Mn 1/3Co 1/3O 2).
Fig. 6 does not coat and coated Si O 2LiNi 1/3Mn 1/3Co 1/3O 2The cycle performance figure of lithium ion anode material (a, not coated Si O 2LiNi 1/3Mn 1/3Co 1/3O 2B, coated Si O 2LiNi 1/3Mn 1/3Co 1/3O 2).
Fig. 7 does not coat and coated Si O 2LiMn 2O 4The cycle performance figure of lithium ion anode material (a, not coated Si O 2LiMn 2O 4B, coated Si O 2LiMn 2O 4).
Fig. 8 does not coat and coats CoAlPO 4LiNi 0.8Co 0.2O 2(a does not coat CoAlPO to the cycle performance figure of lithium ion anode material 4LiNi 0.8Co 0.2O 2B coats CoAlPO 4LiNi 0.8Co 0.2O 2).
Concrete execution mode
Embodiment 1
Earlier with 100g (1.0217mol) LiCoO 2Lithium ion anode material and 6.53g (0.009799mol) are as the material (Al that coats usefulness 2(SO 4) 318H 2O) ball milling mixed about 30 minutes, added 3.53g (0.08825mol) NaOH pressed powder again and continued ball milling a period of time, made its even mixing; Use the deionized water wash said mixture again,, and then, promptly obtain Al in 700 ℃ of roastings 3 hours in 100 ℃ of oven dry 2O 3Surface coated LiCoO 2Lithium ion anode material.
Embodiment 2:
Earlier with 100g (1.0652mol) LiMn 2O 4Lithium ion anode material and 0.38g (0.001353mol) are as the material (CoSO that coats usefulness 47H 2O) ball milling mixed about 30 minutes, added 0.52g (0.001368mol) Na then 3PO 412H 2O pressed powder ball milling a period of time makes its even mixing, uses the deionized water wash said mixture again, in 100 ℃ of oven dry, in 700 ℃ of roastings 3 hours, promptly obtains Co again 3(PO 4) 2The LiMn that coats 2O 4Lithium ion anode material.
Embodiment 3
Earlier with 100g (1.0237mol) LiNi 0.8Co 0.2O 2Lithium ion anode material and 4.1g (0.006152mol) are as the material (Al that coats usefulness 2(SO 4) 318H 2O) ball milling mixed about 40 minutes, added 3.12g (0.008208mol) Na then 3PO 412H 2O pressed powder ball milling a period of time makes its even mixing, uses the deionized water wash said mixture again, in 50-120 ℃ of oven dry, obtains AlPO in 4 hours in 650 ℃ of roastings again 4Surface coated LiNi 0.8Co 0.2O 2Lithium ion anode material.
Embodiment 4
Earlier with 100g (1.03668mol) LiNi 1/3Mn 1/3Co 1/3O 2Lithium ion anode material and 4.72g (0.01661mol) are as the material (Na that coats usefulness 2SiO 49H 2O) ball milling mixed about 40 minutes, added 4g (0.07477mol) NH again 4Cl pressed powder ball milling a period of time makes its even mixing, uses the deionized water wash said mixture again, in 100 ℃ of oven dry, in 400 ℃ of roastings 4 hours, promptly obtains SiO again 2Surface coated LiNi 1/3Mn 1/3Co 1/3O 2Lithium ion anode material.
Embodiment 5
Earlier with 100g (1.0652mol) LiMn 2O 4Lithium ion anode material and 14.16g (0.04983mol) are as the material (Na that coats usefulness 2SiO 49H 2O) ball milling mixed about 40 minutes, added 12g (0.22431mol) NH again 4Cl pressed powder ball milling a period of time makes its even mixing, uses the deionized water wash said mixture again, in 100 ℃ of oven dry, in 400 ℃ of roastings 4 hours, promptly obtains SiO again 2Surface coated LiMn 2O 4Lithium ion anode material.
Embodiment 6
Earlier with 100g (1.0237mol) LiNi 0.8Co 0.2O 2Lithium ion anode material and conduct coat 2.046g (the 0.00307mol) (Al of usefulness 2(SO 4) 318H 2O) and 1.74g (0.006173mol) (CoSO 47H 2O) the material ball milling mixed about 40 minutes, added 2.59g (0.006814mol) Na then 3PO 412H 2O pressed powder ball milling a period of time makes its even mixing, uses the deionized water wash said mixture again, in 50-120 ℃ of oven dry, obtains CoAlPO in 4 hours in 650 ℃ of roastings again 4Surface coated LiNi 0.8Co 0.2O 2Lithium ion anode material.

Claims (6)

1. one kind is carried out surface coated low thermal solid phase method to lithium ion anode material, it is characterized in that: may further comprise the steps:
A: with lithium ion anode material, as slaine that coats usefulness and the pressed powder that can carry out low fever solid phase reaction with it, by 1: (0.001-0.3): (0.001-0.3) mixed in molar ratio, ball milling make its even mixing, get mixture;
B: use the deionized water wash said mixture, the lithium ion anode material that obtains coating in 50-120 ℃ of oven dry;
C: the lithium ion anode material product that the lithium ion anode material after the above-mentioned oven dry was obtained coating in 400-850 ℃ of roasting 0.5-6 hour again.
2. according to claim 1ly a kind of lithium ion anode material is carried out surface coated low thermal solid phase method, it is characterized in that: be selected from a kind of in Si, Mg, Al, Ti, Ni, Mn, Co, Ce, Y, the Fe slaine or several combination under compatible situation as the material that coats usefulness, its fusing point of described slaine must be lower than 300 ℃.
3. require describedly a kind of lithium ion anode material to be carried out surface coated low thermal solid phase method according to right 1, it is characterized in that: described pressed powder is selected from LiOHH 2O, NaOH, Na 2CO 3, NH 4A kind of among the Cl or several combination under compatible situation.
4. require describedly a kind of lithium ion anode material to be carried out surface coated low thermal solid phase method according to right 3, it is characterized in that: a kind of in Mg, Al, Ti, Ni, Mn, Co, Ce, Y, the Fe slaine or several combination energy and LiOHH under compatible situation 2O, NaOH, Na 2CO 3, Na 3PO 4In a kind of or under compatible situation several combinations react; The slaine of Si and NH 4The Cl reaction.
5. according to claim 1ly a kind of lithium ion anode material is carried out surface coated low thermal solid phase method, it is characterized in that: lithium ion anode material is LiCoO 2, LiMn 2O 4, LiFePO 4, LiNi 1/3Mn 1/3Co 1/3O 2, LiNi 1-xCo xO 2(x＜1) or LiNi 1-xM xO 2(M is a doping metals, x＜1).
6. according to claim 1ly a kind of lithium ion anode material is carried out surface coated low thermal solid phase method, it is characterized in that: coating is for by the 0.1-5wt% of coated lithium ion positive electrode, by percentage to the quality.
CNB2007100355719A 2007-08-16 2007-08-16 A low thermal solid phase method for coating the surface of lithium ion cathode material Expired - Fee Related CN100470889C (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102163709A (en) * 2011-03-09 2011-08-24 合肥工业大学 Cobalt nickel manganese lithium oxide-cooper oxide compound positive material for lithium ion battery and preparation method thereof
CN102324515A (en) * 2011-09-20 2012-01-18 湖南升华科技有限公司 The lithium manganate having spinel structure preparation method reaches by its LiMn2O4 that makes and battery
CN103178259A (en) * 2013-02-04 2013-06-26 湖南桑顿新能源有限公司 Preparation method of cobalt-coated lithium ion battery anode material
CN103996842A (en) * 2014-05-20 2014-08-20 常州大学 Method for improving performance of electrode material LNMO
CN105562003A (en) * 2016-01-29 2016-05-11 太原理工大学 Synthesis gas methanation catalyst and preparation method and application
CN108232150A (en) * 2017-12-29 2018-06-29 贵州振华义龙新材料有限公司 Anode material for lithium-ion batteries and its preparation method and application
CN108598382A (en) * 2018-03-07 2018-09-28 电子科技大学 A kind of method of watery fusion coated lithium ion battery positive electrode
CN114243100A (en) * 2021-08-30 2022-03-25 上海大学 Positive electrode metal salt additive capable of being used for positive electrode interface film construction of solid electrolyte and application thereof
CN115148997A (en) * 2022-09-05 2022-10-04 宁德时代新能源科技股份有限公司 Composite positive electrode active material, method for producing same, and electricity-using device comprising same

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102163709A (en) * 2011-03-09 2011-08-24 合肥工业大学 Cobalt nickel manganese lithium oxide-cooper oxide compound positive material for lithium ion battery and preparation method thereof
CN102163709B (en) * 2011-03-09 2013-01-09 合肥工业大学 Cobalt nickel manganese lithium oxide-cooper oxide compound positive material for lithium ion battery and preparation method thereof
CN102324515A (en) * 2011-09-20 2012-01-18 湖南升华科技有限公司 The lithium manganate having spinel structure preparation method reaches by its LiMn2O4 that makes and battery
CN102324515B (en) * 2011-09-20 2014-06-11 湖南升华科技有限公司 Spinel type lithium manganate and preparation method thereof as well as battery
CN103178259A (en) * 2013-02-04 2013-06-26 湖南桑顿新能源有限公司 Preparation method of cobalt-coated lithium ion battery anode material
CN103996842A (en) * 2014-05-20 2014-08-20 常州大学 Method for improving performance of electrode material LNMO
CN105562003A (en) * 2016-01-29 2016-05-11 太原理工大学 Synthesis gas methanation catalyst and preparation method and application
CN108232150A (en) * 2017-12-29 2018-06-29 贵州振华义龙新材料有限公司 Anode material for lithium-ion batteries and its preparation method and application
CN108598382A (en) * 2018-03-07 2018-09-28 电子科技大学 A kind of method of watery fusion coated lithium ion battery positive electrode
CN114243100A (en) * 2021-08-30 2022-03-25 上海大学 Positive electrode metal salt additive capable of being used for positive electrode interface film construction of solid electrolyte and application thereof
CN114243100B (en) * 2021-08-30 2024-05-14 上海大学 Positive electrode metal salt additive capable of being used for construction of positive electrode interface film of solid electrolyte and application thereof
CN115148997A (en) * 2022-09-05 2022-10-04 宁德时代新能源科技股份有限公司 Composite positive electrode active material, method for producing same, and electricity-using device comprising same
WO2024051216A1 (en) * 2022-09-05 2024-03-14 宁德时代新能源科技股份有限公司 Composite positive electrode active material, preparation method therefor, and electric device comprising composite positive electrode active material

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