CN103078099A - Anode material for lithium ion cell and preparation method thereof - Google Patents

Anode material for lithium ion cell and preparation method thereof Download PDF

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Publication number
CN103078099A
CN103078099A CN2012105818224A CN201210581822A CN103078099A CN 103078099 A CN103078099 A CN 103078099A CN 2012105818224 A CN2012105818224 A CN 2012105818224A CN 201210581822 A CN201210581822 A CN 201210581822A CN 103078099 A CN103078099 A CN 103078099A
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China
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preparation
lithium
anode material
positive electrode
manganese
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CN2012105818224A
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孟海星
金慧芬
高俊奎
步绍宁
王硕
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Tianjin Lishen Battery JSCL
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Tianjin Lishen Battery JSCL
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention belongs to the technical field of lithium ion cells, and specifically discloses an anode material for a high-energy-density lithium ion cell with excellent performance and a preparation method for the anode material. The chemical expression formula of the anode material for the lithium ion cell is Li1+XM1-XO2, wherein the M represents three metallic elements of nickel, cobalt and manganese, and a proportion of the three metallic elements of nickel, cobalt and manganese is 0.21:0.12:0.67; and the X is larger than or equal to 0.17 and smaller than or equal to 0.25. The preparation method comprises the steps that transition metal salt precursors containing the three metallic elements of nickel, cobalt and manganese are prepared by a coprecipitation method, and then after the transition metal salt precursors are uniformly mixed with lithium salt with a wet method in proportion, the anode material is obtained by calcination at a high temperature. According to the invention, the specific capacity of the prepared anode material for the lithium ion cell is higher than 250mAh/g, so that the anode material has lower first irreversible capacity and excellent circulatory stability performance.

Description

A kind of anode material for lithium-ion batteries and preparation method thereof
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of anode material for lithium-ion batteries and preparation method thereof.
Background technology
Lithium rechargeable battery is nineteen ninety by the take the lead in novel green high-power rechargeable battery successfully released of Sony corporation of Japan, it is current internationally recognized desirable chemical power source, have voltage height, energy density large, have extended cycle life, the many merits such as self discharge is little, memory-less effect, operating temperature range are wide, pollution-free, be widely used in mobile phone, laptop computer, portable power tool, weaponry etc.Growing along with lithium ion battery has high-energy-density, high power density, high safety and the low-cost study hotspot that becomes the lithium battery field.
As one of lithium ion battery key function material, positive electrode is the source of lithium ion in the battery, and its performance is directly connected to battery performance, is lithium electric flux density basis.Business-like positive electrode specific capacity does not also surpass 200mAh/g at present, has seriously restricted the development process of high performance lithium ion battery of new generation.
Lithium-rich manganese-based layered cathode material causes great concern because it has height ratio capacity, is considered to the anodal candidate material of the lithium ion battery with high energy density of at present tool prospect.U.S. Argonne laboratory in 2004 with the lithium-rich manganese-based layered cathode material openly report that is the theme first: a kind of xLi[Li is disclosed in US Patent No. 6677082 1/3Mn 2/3] O 2. (1-x) LiMO 2(M is transition metal, 0<=X<=1) lithium-rich manganese-based solid-solution material.The chemical general formula of such material is Li 1+xM 1-xO 2(M=Co, Ni, the combination of the various metals atoms such as Mn), structure and α-NaFeO 2The stratiform configuration is identical, belongs to hexagonal crystal system, the R-3m space group.Theoretical specific capacity is greater than 300mAh/g, and actual specific capacity is greater than 200mAh/g.Among the Chinese patent CN03126255.4 in disclosed such material first discharge specific capacity can reach 181mAh/g, put first specific capacitance and can reach 90% of its charge ratio capacity, the stoichiometric equation lithium of material is 1.1:1 with the ratio of the atomic weight of nickel, cobalt, manganese in this patent, and the ratio of the atomic weight of three kinds of elements of nickel cobalt manganese is 1; A kind of preparation method of such material is disclosed among the Chinese patent CN200410101824.4, the preparation method of this material doped Al or doping metals Cr is disclosed in the patent, be used for improving the chemical property of material, but in patent, do not see the chemical property data of prepared material; A kind of synthetic method of such material is disclosed in Chinese patent CN201110111035.9 in addition, and utilize respectively sodium peroxydisulfate and potassium peroxydisulfate that this material has been carried out surface treatment, the first discharge specific capacity of material is respectively 242mAh/g and 234mAh/g after processing, efficiency for charge-discharge is 82.3% and 78.65%, as seen it is lower to pass through after the surface treatment discharge capacity of material, and efficiency for charge-discharge still remains to be improved; Synthesized a kind of chemical Li[Li at published Chinese patent CN201210199500.3 0.167Ni 0.166Co 0.166Mn 0.500] O 2Such material, first discharge specific capacity is less than 225mAh/g, discharge capacity is lower first, the cycle performance of illustrative material not in this patent.
In sum, lithium-rich manganese-based anode material has represented good application prospect, is one of required critical material of high specific energy lithium ion battery of future generation.But also there are problems for practical application: meeting precipitated oxygen in (1) material initial charge, material structure changes, and causes the relatively poor and larger irreversible capacity of cyclical stability; (2) material is through after repeatedly discharging and recharging, and the voltage platform decline is serious; (3) electric conductivity of material is relatively poor, is unfavorable for high current charge-discharge.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art and high specific energy anode material for lithium-ion batteries of a kind of excellent performance and preparation method thereof is provided.
The present invention is achieved in that a kind of anode material for lithium-ion batteries, and it is as follows that its chemistry is expressed general formula:
Li 1+XM 1-XO 2
Wherein, M represents nickel, cobalt, three kinds of metallic elements of manganese, and the ratio of these three kinds of metallic elements is 0.21:0.12:0.67,0.17≤X≤0.25.
The preparation method of described anode material for lithium-ion batteries may further comprise the steps:
1) utilize coprecipitation to prepare the transition metal salt precursor
Nickeliferous, the cobalt of mol ratio 0.21:0.12:0.67, the analytical pure sulfuric acid salt of manganese metallic element are dissolved in the deionized water, and forming metallic element concentration is the solution of 2mol/L; Aforementioned solution is added in the reactor, then precipitation reagent is slowly added in the reactor, at 7.5-7.7, carry out coprecipitation reaction with basic species regulator solution pH value; The sediment of getting the coprecipitation reaction generation obtains described transition metal salt presoma with the rear drying of deionized water washing;
2) utilize solid reaction process to prepare positive electrode
1.4:1 passes through the evenly rear high temperature sintering of wet-mixed with lithium source and described transition metal salt presoma in molar ratio, obtains this positive electrode.
Described precipitation reagent is carbonate.
Described carbonate is selected from a kind of in sodium carbonate, the lithium carbonate.
Described lithium source is selected from a kind of of lithium carbonate, lithium acetate, lithium hydroxide.
Described basic species is selected from a kind of in potassium hydroxide, NaOH, the ammoniacal liquor.
Among the present invention, the coprecipitation reaction time is greater than 14h.
Among the present invention, during high temperature sintering, at first at 500 ℃ of pre-thermal sintering 8h, then at 800 ℃ ~ 900 ℃ lower sintering 12h.
Among the present invention, high temperature sintering adopts box Muffle furnace.
Anode material for lithium-ion batteries of the present invention has larger specific discharge capacity, and under the condition without any finishing, discharging efficiency is greatly improved first, reduced the first irreversible capacity of material, cycle performance is better, be conducive to promote lithium-rich manganese-based anode material application in practice, be of great practical significance.
Description of drawings
Fig. 1 is the XRD of the positive electrode of embodiment 1 ~ 3 preparation;
Fig. 2 is the SEM of the positive electrode of embodiment 1 ~ 3 preparation;
Fig. 3 is the first charge-discharge curve of the test battery made of the positive electrode of embodiment 1 ~ 3 preparation;
Fig. 4 is the cycle performance curve of the test battery made of the positive electrode of embodiment 2 preparation.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing, the present invention is further elaborated.
Anode material for lithium-ion batteries of the present invention, it is as follows that its chemistry is expressed general formula:
Li 1+XM 1-XO 2
Wherein, M represents nickel, cobalt, three kinds of metallic elements of manganese, and the ratio of these three kinds of metallic elements is 0.21:0.12:0.67,0.17≤X≤0.25.
Described lithium ion anode material can be a kind of of following chemical formulation:
Li 1.17(Ni 0.21Co 0.12Mn 0.67) 0.83O 2、Li 1.2(Ni 0.21Co 0.12Mn 0.67) 0.80O 2、Li 1.23(Ni 0.21Co 0.12Mn 0.67) 0.77O 2、Li 1.26(Ni 0.21Co 0.12Mn 0.67) 0.74O 2
The preparation of described positive electrode:
Embodiment 1
1) utilize coprecipitation to prepare the transition metal salt precursor
Getting mol ratio is the transiting metal nickel that contains of 0.21:0.12:0.67, cobalt, three kinds of metallic elements of manganese have analytically pure sulfate, be dissolved in the appropriate amount of deionized water, forming the metallic element ion concentration is the solution of 2mol/L, then this solution is added in the 5L glass reaction still, the speed that stirs in the conditioned reaction still is 400rpm, conditioned reaction still bath temperature is 55 ℃, utilize peristaltic pump that carbonate is joined in the reactor, and the pH value of regulator solution, make it 7.6, control suitable feed rate, reaction time is controlled to be 14h, filters above-mentioned suspension, gets precipitation and partly and with deionized water washs, 100 ℃ of dry 12h in air, after obtain crossing the slaine precursor;
2) utilize solid reaction process to prepare positive electrode
With lithium hydroxide with to cross the slaine presoma be the 1.4:1 ratio according to mol ratio, it is even to utilize planetary ball mill to carry out wet-mixed, select alcohol to do dispersant, with drying under the 80 ℃ of conditions of material that mix, utilize Muffle furnace to carry out high temperature sintering, during sintering, first at 500 ℃ of pre-burning 8h, then at 800 ℃ of high temperature sintering 12h, intensification, rate of temperature fall are respectively 2 ℃/min and 5 ℃/min in sintering process, and the chemical formula of the positive electrode that forms behind the sintering is Li 1.17(Ni 0.21Co 0.12Mn 0.67) 0.83O 2
The ball mill container that described planetary ball mill is used can be corundum ball grinder, agate jar, polyurethane ball-milling pot, nylon ball grinder or tungsten-carbide ball grinding jar, and the ball that used ball grinder has has zirconia ball, corundum ball, agate ball, polyurethane ball.
Embodiment 2
Method according to embodiment 1 prepares this anode material for lithium-ion batteries, and the temperature of high temperature sintering changes at 850 ℃ of high temperature sintering 12h.
Embodiment 3
Method according to embodiment 1 prepares this anode material for lithium-ion batteries, and the temperature of high temperature sintering changes at 900 ℃ of high temperature sintering 12h.
The present invention adopts CR2430 type button half-cell to estimate each embodiment 1 ~ 3 resulting cell positive material.This CR2430 type button half-cell battery includes positive plate, negative plate, barrier film and electrolyte.Described positive plate includes plus plate current-collecting body, at plus plate current-collecting body surface-coated one deck positive electrode material layer.Wherein, described plus plate current-collecting body is aluminium foil, and described positive electrode material layer comprises positive electrode of the present invention, binding agent and solvent; Described binding agent includes a kind of in polytetrafluoroethylene, poly-inclined to one side tetrafluoroethene, phenolic resins, polyvinyl alcohol and the polyvinylpyrrolidone; Described solvent is N-crassitude ketone solvent; Described negative plate is the lithium sheet; Described electrolyte comprises electrolyte and anhydrous solvent, and described electrolyte is selected from hexafluoroarsenate lithium LiAsF 6, lithium hexafluoro phosphate LiPF 6, lithium perchlorate LiClO 4, LiBF4 LiBF 4In a kind of; Described anhydrous solvent includes a kind of in ethylene carbonate, propene carbonate, the dimethyl carbonate; The environment of half-cell preparation is drying room.
The making step of described CR2430 type button half-cell battery is as follows:
Take by weighing respectively the described positive electrode of the embodiment of the invention, conductive agent and binding agent in small-sized homogenate tank for 90:5:5 in mass ratio, add N-methyl pyrrolidone as solvent, obtain the slurry of certain viscosity and solid content by stirring; With spreader with the slurry that obtains scrape on the tenaplate plus plate current-collecting body, oven dry, cut obtain suitable size disk as Electrode; Then adopt traditional button cell assembly technology to encapsulate, to be measured.
Anode material for lithium-ion batteries (showing as black powder) by embodiment 1 ~ 3 preparation is characterized by the physical property of the testing equipments such as X-ray diffraction (XRD) instrument, scanning electron microscopy (SEM), EDS to positive electrode, utilize blue electric system that the chemical property of the battery of the described positive electrode making of the embodiment of the invention is measured, material discharges and recharges under the 0.05C condition, and data see the following form 1.
The chemical property data of table 1 material
Fig. 1 is the XRD figure of the positive electrode of embodiment 1 ~ 3 preparation, the as seen from Figure 1 structure of positive electrode and LiNiO 2Structure is coincide, and shows as layer structure, can think and α-NaFeO 2The stratiform configuration is substantially identical, and the crystal property of material is better, at the 20-25 degree assorted peak is arranged in addition, can find out that the assorted peak of this diffraction is along with the raising of sintering temperature dies down, the degree of crystallinity that positive electrode is described is relevant with temperature, and along with the raising of sintering temperature, the crystal property of positive electrode improves.
Fig. 2 from left to right is respectively the SEM of positive electrode of the preparation of embodiment 1 ~ 3, can find out in the positive electrode distribution of particles of 850 ℃ of sintering more evenly, and positive electrode synthetic under this temperature has good chemical property.
The first discharge capacity of the battery that the positive electrode that Fig. 3 and table 1 sinter into greater than other two kinds of temperature in conjunction with the first discharge capacity that can see clearly the test battery that positive electrode is made behind 850 ℃ of sintering is made, and has less irreversible capacity, think that the positive electrode structure when 850 ℃ of sintering is more stable, the positive electrode crystal transfer of sintering is smaller under this temperature in the charge and discharge process of battery, and the specific capacity recovery rate is larger.
Fig. 4 can find out the cycle performance of the lithium ion test battery that adopts the described positive electrode of the embodiment of the invention (850 ℃ of sintering) making, in this Fig. 4, specific discharge capacity was still at 230mAh/g after the test battery that the described positive electrode of the embodiment of the invention is made circulated through 20 times.Illustrate that the described positive electrode of the embodiment of the invention has good cycle performance, show the Stability Analysis of Structures of the described positive electrode of the embodiment of the invention, changes in crystal structure is less in the test battery charge and discharge process.
The present invention measures the parameters such as ratio, the sintering temperature of optimizing the positive electrode preparation, sintering time by transition metal and lithium metallic atom in the optimization positive electrode, thereby the lithium-rich manganese-based anode material that has prepared function admirable, the specific discharge capacity of positive electrode and the cycle performance of material have been improved, realized that production, teaching ﹠ research combines, for this material use synthetic that move towards the industrialization provides guidance, be of great practical significance.
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.

Claims (9)

1. an anode material for lithium-ion batteries is characterized in that, it is as follows that its chemistry is expressed general formula:
Li 1+XM 1-XO 2
Wherein, M represents nickel, cobalt, three kinds of metallic elements of manganese, and the ratio of these three kinds of metallic elements is 0.21:0.12:0.67,0.17≤X≤0.25.
2. the preparation method of the described anode material for lithium-ion batteries of claim 1 is characterized in that, may further comprise the steps:
1) utilize coprecipitation to prepare the transition metal salt precursor
Nickeliferous, the cobalt of mol ratio 0.21:0.12:0.67, the analytical pure sulfuric acid salt of manganese metallic element are dissolved in the deionized water, and forming metallic element concentration is the solution of 2mol/L; Aforementioned solution is added in the reactor, then precipitation reagent is slowly added in the reactor, at 7.5-7.7, carry out coprecipitation reaction with basic species regulator solution pH value; The sediment of getting the coprecipitation reaction generation obtains described transition metal salt presoma with the rear drying of deionized water washing;
2) utilize solid reaction process to prepare positive electrode
1.4:1 passes through the evenly rear high temperature sintering of wet-mixed with lithium source and described transition metal salt presoma in molar ratio, obtains this positive electrode.
3. preparation method according to claim 2 is characterized in that, described precipitation reagent is carbonate.
4. preparation method according to claim 3 is characterized in that, described carbonate is selected from a kind of in sodium carbonate, the lithium carbonate.
5. preparation method according to claim 2 is characterized in that, described lithium source is selected from a kind of of lithium carbonate, lithium acetate, lithium hydroxide.
6. preparation method according to claim 2 is characterized in that, described basic species is selected from a kind of in potassium hydroxide, NaOH, the ammoniacal liquor.
7. preparation method according to claim 2 is characterized in that, the coprecipitation reaction time is greater than 14h.
8. preparation method according to claim 2 is characterized in that, during high temperature sintering, at first at 500 ℃ of pre-thermal sintering 8h, then at 800 ℃ ~ 900 ℃ lower sintering 12h.
9. preparation method according to claim 2 is characterized in that, high temperature sintering adopts box Muffle furnace.
CN2012105818224A 2012-12-27 2012-12-27 Anode material for lithium ion cell and preparation method thereof Pending CN103078099A (en)

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Cited By (7)

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CN103594682A (en) * 2013-10-23 2014-02-19 江苏大学 Preparation method of lithium ion battery solid solution positive pole material
CN105489876A (en) * 2014-09-15 2016-04-13 无锡晶石新型能源有限公司 Production method of composite cathode material for lithium ion battery
CN107001068A (en) * 2014-11-26 2017-08-01 巴斯夫欧洲公司 Method for preparing lithiated transition metal oxides
CN107017405A (en) * 2017-06-16 2017-08-04 湖南师范大学 A kind of anode material for lithium-ion batteries and preparation method thereof
CN107910529A (en) * 2017-11-18 2018-04-13 桂林电子科技大学 A kind of ternary cathode material of lithium ion battery of manganese Base Metal organic frame compound cladding and preparation method thereof
CN111106340A (en) * 2018-10-26 2020-05-05 中国科学院大连化学物理研究所 Lithium ion battery anode material and preparation and application thereof
CN111217407A (en) * 2020-01-16 2020-06-02 东莞东阳光科研发有限公司 High-nickel anode material and preparation method and application thereof

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CN102683645A (en) * 2011-03-17 2012-09-19 中国科学院宁波材料技术与工程研究所 Preparation method of layered lithium-rich manganese base oxide of positive material of lithium ion battery

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103594682A (en) * 2013-10-23 2014-02-19 江苏大学 Preparation method of lithium ion battery solid solution positive pole material
CN105489876A (en) * 2014-09-15 2016-04-13 无锡晶石新型能源有限公司 Production method of composite cathode material for lithium ion battery
CN107001068A (en) * 2014-11-26 2017-08-01 巴斯夫欧洲公司 Method for preparing lithiated transition metal oxides
US10526213B2 (en) 2014-11-26 2020-01-07 Basf Se Process for making a lithiated transition metal oxide
US10836650B2 (en) 2014-11-26 2020-11-17 Basf Se Process for making a lithiated transition metal oxide
CN107017405A (en) * 2017-06-16 2017-08-04 湖南师范大学 A kind of anode material for lithium-ion batteries and preparation method thereof
CN107910529A (en) * 2017-11-18 2018-04-13 桂林电子科技大学 A kind of ternary cathode material of lithium ion battery of manganese Base Metal organic frame compound cladding and preparation method thereof
CN111106340A (en) * 2018-10-26 2020-05-05 中国科学院大连化学物理研究所 Lithium ion battery anode material and preparation and application thereof
CN111106340B (en) * 2018-10-26 2021-05-07 中国科学院大连化学物理研究所 Lithium ion battery anode material and preparation and application thereof
CN111217407A (en) * 2020-01-16 2020-06-02 东莞东阳光科研发有限公司 High-nickel anode material and preparation method and application thereof

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