CN100524905C - Method for improving secondary lithium ion battery cathode material safety performance - Google Patents
Method for improving secondary lithium ion battery cathode material safety performance Download PDFInfo
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- CN100524905C CN100524905C CNB2005100351846A CN200510035184A CN100524905C CN 100524905 C CN100524905 C CN 100524905C CN B2005100351846 A CNB2005100351846 A CN B2005100351846A CN 200510035184 A CN200510035184 A CN 200510035184A CN 100524905 C CN100524905 C CN 100524905C
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- aluminium
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- 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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a method for improving the performance of secondary lithium battery cathode material. The method comprises steps of: mixing aluminium salts with transition metal oxide that as secondary lithium cathode active materials; baking the mixture in high temperature and eluting with strong alkaline solution; removing the rest alkaline solution with water or hydrophilic agent. The invention combines present coating and doping processes: after solid state reaction, forming an aluminum oxide coating on the secondary lithium cathode active material; forming aluminum doping in the contact area of aluminum oxide and cathode active material; removing rest aluminium oxide with alkali to improve the voltage of cathode active material oxidation electrolytic solution.
Description
Technical field:
The present invention relates to after polymerization thing technical field of lithium batteries, relate to a kind of method of improving secondary lithium ion battery cathode material safety performance in particular.
Background technology:
Secondary lithium battery has attracted battery researcher and producer with advantages such as its high-energy, high reliability, good processability and non-environmental-pollutions always strongly since it comes out.The battery of secondary lithium battery mainly comprises cathode sheets, barrier film and the anode strip of mutual superposition, and wherein cathode sheets comprises cathode current collector and diaphragm attached thereto, that have the movable material of negative electrode.As the active material of cathode of nonaqueous secondary lithium battery, using now and studying is the transition region metal oxide that contains lithium the most widely.Relatively be typically two kinds of crystal structures now, the one, with cobalt acid lithium (LiCoO
2) be the structure of representative, for example lithium nickelate (LiNiO
2), LiNi
1/3Co
1/3Mn
1/3O
2Deng.Another structure is with LiMn2O4 (LiMn
2O
4) for the spinel structure of representative.Hereinafter said cathode active material is exactly above-mentioned two class materials.But the active material of these two kinds of structures is in overheated or superpotential condition, all can oxidation electrolyte, and emit a large amount of heat, thereby cause the thermal runaway of battery and cause safety problem.Especially be the material of representative with cobalt acid lithium, when overvoltage, also can emit oxygen and aggravate oxidation.Problem for this respect, industry has two kinds of methods to improve security performance, the first improves the stability of material by the method for oxide coated on surface, Yong Jeong Kim etc. for example, in 2002 at Journal of The Electrochemical Society, the article of delivering on 149 (10) A1337-A1314, (ZnO) improves fail safe by zinc oxide.Other method is to improve security performance by the method for mixing.Meijing Zou etc. for example, in 2004 at Electrochemical and Solid-State Letters, 7 (7) A176-A179 publish an article and propose to improve fail safe with aluminium, titanium and magnesium etc. by the mode of doping.These two kinds of methods respectively have the shortcoming of oneself: the method that oxide is covered on the surface can hinder the surface area that lithium ion passes in and out active material owing to too many oxide.And the increase internal resistance reduces the discharge capability of big electric current, can cause very little coating not exclusively, and do not reach improve effect; Doping method is introduced assorted element and is realized that the uniformity of this method doped chemical is difficult to control when cathode active material is synthetic.
Summary of the invention:
Technical problem to be solved by this invention refers to overcoming the shortcoming of the said goods, in conjunction with present technology, provides a kind of method of improving secondary lithium ion battery cathode material safety performance.
For solving technique scheme, the present invention has adopted following technical scheme: its method may further comprise the steps: at first, be basic material to contain transition region metal oxide lithium, that can be used as the secondary lithium-ion cathode active material; Secondly, basic material and aluminium salt mix, and wherein the content of aluminium salt is 0.5%～50% of basic material; Then, the mixture of aluminium salt and basic material is carried out high-temperature baking, the temperature range of baking is 300～1100 degrees centigrade; Then, with the material that toasted strong base solution drip washing; At last, the alkali lye of water or hydrophilic solvent flush away remnants removes by the method for baking and desolvates.
The present invention combines coating, the two kinds of methods of mixing.At first, form the coating layer of aluminium oxide on the cathode active material surface of secondary lithium battery, also can form the doping of aluminium simultaneously at the contact area of aluminium oxide and cathode active material by the solid phase reaction under the high temperature.Then by highly basic,, thereby improved the chemical property of cathode active material unnecessary aluminium oxide removal.
Embodiment:
It is basic material that the present invention at first needs the transition region metal oxide of cathode active material is provided, and its chemical formula is:
LizMxOy or LizMxN (1-x) Oy wherein M is the transition region metallic element, for example cobalt (Co), manganese (Mn), nickel (Ni) or other transition region metallic element.N is one or more metallic elements, for example nickel (Ni) manganese elements such as (Mn).X, Y and Z are natural numbers.
Secondly, instead can decompose the predecessor that produces aluminium oxide, aluminum nitrate for example, aluminium acetate, aluminium isopropoxide or aluminium oxide are waited until and as the abundant dispersing and mixing of the cathode active material of basic substance of the present invention.(content of aluminium salt be basic material 0.5% to 50%).If use aluminium oxide, recommend to use micron order even nano level, to improve the dispersibility and the respond of aluminium oxide in cathode active material.The method of dispersing and mixing is divided into wet method and dry method.Wet method is that cathode active material is immersed in the solvent that is dissolved with or is dispersed with aluminium salt, adds the deposited salt precipitation then.In wet method, can add thickeners such as citric acid and improve the dispersed uniform that is deposited in the cathode active material powder.Dry method is that the aluminium salt as predecessor is mixed by doing the mode of mixing in cathode active material.
Then, be the aluminium salt that mixes or the product and the cathode active material high-temperature baking of aluminium salt.Temperature will be higher than thermal decomposition of aluminium salt and aluminium salt and cathode active material and carry out the required temperature of solid phase reaction.300～1100 degrees centigrade of recommended temperature.
Then, react away unnecessary aluminium oxide with strong base solution, strong base solution can be selected from NaOH, potassium hydroxide, the ammoniacal liquor of lithium hydroxide.
At last, rinse unnecessary strong base solution, remove by the method for baking again and desolvate.
Embodiment
, cobalt acid lithium 100 grams are immersed in 30% aluminum nitrate solution 70 grams as basic material with cobalt acid lithium, add citric acid 7 grams, add ammoniacal liquor and regulate pH value to 10,100 degrees centigrade of bakings 3 hours, 500 degrees centigrade of bakings in 5 hours.NaOH 40 grams with 10% carry out drip washing.Be rinsed in the water after the drip washing sodium ion less than 100PPM with deionized water then.The sample that obtains is made button cell carry out loop test (3.0～4.5 volts of voltage ranges).
| The circulation sequence number | Charging/mAh | Discharge/mAh | Charging/mAh/g | Discharge/mAh/g | Efficient/% |
| 1 | 5.61 | 5.38 | 200.0 | 191.8 | 95.9 |
| 2 | 5.44 | 5.36 | 193.8 | 191.1 | 98.6 |
| 3 | 5.40 | 5.34 | 192.6 | 190.4 | 98.9 |
| 4 | 5.36 | 5.31 | 191.2 | 189.4 | 99.0 |
| 5 | 5.35 | 5.31 | 190.7 | 189.2 | 99.2 |
| 6 | 5.33 | 5.28 | 190.1 | 188.2 | 99.0 |
| 7 | 5.29 | 5.25 | 188.6 | 187.2 | 99.2 |
| 8 | 5.28 | 5.24 | 188.3 | 186.8 | 99.2 |
| 9 | 5.26 | 5.23 | 187.5 | 186.4 | 99.4 |
| 10 | 5.26 | 5.22 | 187.5 | 186.1 | 99.3 |
| 11 | 5.24 | 5.18 | 186.8 | 184.8 | 98.9 |
| 12 | 5.24 | 5.18 | 186.7 | 184.6 | 98.9 |
| 13 | 5.21 | 5.17 | 185.6 | 184.2 | 99.2 |
Claims (6)
1, improves the method for secondary lithium ion battery cathode material safety performance, the steps include:
One, be basic material to contain transition region metal oxide lithium, that can be used as the secondary lithium battery cathode active material;
Two, basic material and aluminium salt and/or aluminium oxide mix, and wherein the quality of aluminium salt and/or aluminium oxide is 0.5%～50% of a basic material quality;
Three, the mixture with aluminium salt and/or aluminium oxide and basic material carries out high-temperature baking, and the temperature range of baking is 300～1100 degrees centigrade;
One or more solution drip washing in the composite material that four, will toast NaOH, potassium hydroxide, lithium hydroxide and the ammoniacal liquor;
Five, the alkali lye of water or hydrophilic solvent flush away remnants.
2, the method for improving secondary lithium ion battery cathode material safety performance according to claim 1, it is characterized in that: the chemical formula of described basic material is:
Li
ZM
XO
Y, wherein M is the transition region metallic element; X, Y and Z are natural numbers.
3, the method for improving secondary lithium ion battery cathode material safety performance according to claim 1, it is characterized in that: described aluminium salt is one or more in following the enumerating: aluminum nitrate, aluminium carbonate inorganic aluminate, aluminium acetate, aluminium isopropoxide, aluminum stearate organic aluminium salt.
4, the method for improving secondary lithium ion battery cathode material safety performance according to claim 1, it is characterized in that: the method that basic material mixes with aluminium salt and/or aluminium oxide is a dry mixed, is about to aluminium salt and/or aluminium oxide and the basic material that will coat mixes according to suitable ratio is dried equably.
5, the method for improving secondary lithium ion battery cathode material safety performance according to claim 1, it is characterized in that: the method that basic material mixes with aluminium salt and/or aluminium oxide is a wet-mixed, being about to aluminium salt and/or alumina dissolution makes solution or aluminium salt and/or aluminium oxide and solvent is made suspension-turbid liquid in suitable solvent, again solution or suspension-turbid liquid are mixed with basic material to be processed, remove and desolvate.
6, the method for improving secondary lithium ion battery cathode material safety performance according to claim 5 is characterized in that: add thickener or/and add precipitation reagent in the described wet-mixed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100351846A CN100524905C (en) | 2005-06-15 | 2005-06-15 | Method for improving secondary lithium ion battery cathode material safety performance |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100351846A CN100524905C (en) | 2005-06-15 | 2005-06-15 | Method for improving secondary lithium ion battery cathode material safety performance |
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|---|---|
| CN1731601A CN1731601A (en) | 2006-02-08 |
| CN100524905C true CN100524905C (en) | 2009-08-05 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007108425A1 (en) * | 2006-03-17 | 2007-09-27 | Sanyo Electric Co., Ltd. | Nonaqueous electrolyte battery and method for manufacturing same |
| WO2007108610A1 (en) * | 2006-03-20 | 2007-09-27 | Lg Chem, Ltd. | Stoichiometric lithium cobalt oxide and method for preparation of the same |
| JP5647734B2 (en) * | 2010-11-30 | 2015-01-07 | エルジー・ケム・リミテッド | Lithium secondary battery |
| CN102315429B (en) * | 2011-08-04 | 2015-10-28 | 深圳市天骄科技开发有限公司 | The preparation method of aluminum-doped material of cathode of lithium ion battery with solid phase process |
| CN103682354B (en) * | 2012-09-18 | 2016-08-10 | 华为技术有限公司 | A kind of all-solid lithium-ion battery compound electrode material and preparation method thereof and all-solid lithium-ion battery |
| CN104701532A (en) * | 2015-02-11 | 2015-06-10 | 江苏科捷锂电池有限公司 | Preparation method of lithium cobaltate positive material coated with nanometer aluminum oxide solid phase |
| CN108511796A (en) * | 2018-03-30 | 2018-09-07 | 武汉艾特米克超能新材料科技有限公司 | A kind of lithium battery and preparation method thereof using organic electrolyte |
| CN109461895A (en) * | 2018-06-29 | 2019-03-12 | 北京当升材料科技股份有限公司 | A kind of preparation method of the nickelic positive electrode of lithium ion battery |
| CN109119611B (en) * | 2018-08-22 | 2021-12-24 | 广东工业大学 | Method for realizing co-modification of ternary cathode material by ion doping and surface coating through one-step method |
| US12002920B2 (en) | 2020-07-29 | 2024-06-04 | Prologium Technology Co., Ltd. | Method for suppressing thermal runaway of lithium batteries |
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Effective date of registration: 20180824 Address after: 352100 Xingang Road, Zhangwan Town, Jiaocheng District, Ningde, Fujian 1 Patentee after: Ningde Amperex Technology Ltd. Address before: 523080 Baima Industrial Zone, Nancheng District, Dongguan, Guangdong Patentee before: Dongguan New Energy Source Electronic Sci-Tech Co., Ltd. |