CN104701522A - Preparation method for modified lithium-manganate positive material of lithium-ion battery - Google Patents
Preparation method for modified lithium-manganate positive material of lithium-ion battery Download PDFInfo
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- CN104701522A CN104701522A CN201310666222.2A CN201310666222A CN104701522A CN 104701522 A CN104701522 A CN 104701522A CN 201310666222 A CN201310666222 A CN 201310666222A CN 104701522 A CN104701522 A CN 104701522A
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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
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- 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
Abstract
The invention discloses a preparation method for a modified lithium-manganate positive material of a lithium-ion battery. The preparation method comprises the following specific steps: (1) synthesizing a precursor by adopting a liquid-phase temperature-difference method so as to obtain aluminium-doped manganese-carbonate precursor powder; (2) calcining the obtained precursor manganese-carbonate powder for 2-5 hours under the temperature of 600-800 DEG C, so as to obtain an aluminium-doped manganese-oxide powder with a spherical ion-hole structure and the particle diameter being 1-3 microns; (3) uniformly mixing the aluminium-doped manganese-carbonate precursor powder and lithium carbonate according to the ratio of (1 to 1)-(1.05 to 1), maintaining the temperature for 20 hours under the temperature of 900 DEG C, cooling, grinding, repeating the process from roasting to grinding for 3 times, so as to obtain spinel modified lithium-manganate positive material sample with the particle diameter being 1-2 microns. The preparation method disclosed by the invention has the advantages that the raw materials are low in cost and easy to obtain, the microstructure is regular and uniform, the doping effect is good, and the prepared modified lithium manganate is obvious in charging and discharging performances and good in circularity.
Description
Technical field
The invention belongs to field of lithium ion battery material, relate to a kind of method for preparing anode material of lithium-ion battery, particularly a kind of preparation method of modified lithium manganate cathode material.Belong to field of lithium ion battery material.
Technical background
Along with the continuous aggravation of energy crisis, oil price rises violently, and with vapour Vehicular dynamic battery for representative, the new lithium ion battery applications field that market capacity is larger is formed fast, and lithium ion battery is faced with a larger high speed development opportunity.Motive force of development automobile is the direction of China's development of automobile industry.The core of electric automobile is electrokinetic cell.Development safety-type, high performance lithium ion battery, with replacement nickel hydrogen battery, being developing direction and the inexorable trend of vapour Vehicular dynamic battery, is also the objective demand of power vehicle industry development.
Because spinelle LiMn
2o
4there is low, the easy synthesis of cost, operating voltage be high, security performance is high, environmentally safe and have the advantages such as higher capacity, be considered to very potential lithium ion power battery cathode material, abroad some developed countries are by spinel-type LiMn
2o
4material is used as the pure power of EV(), HEV(hybrid power) positive electrode of battery.Domesticly to start late, the spinelle LiMn of the high safety of development low cost
2o
4lithium ion battery is the important directions of electrokinetic cell development from now on.But LiMn
2o
4capacity fade problem be always restriction its bottleneck as the large-scale application of dynamic lithium battery positive electrode.
Summary of the invention
The problem that the present invention solves is LiMn
2o
4capacity fade problem constrain its development in dynamic lithium battery field; For solving described problem, the invention provides a kind of preparation method of lithium ion battery modified lithium manganate cathode material.
The preparation method of lithium ion battery modified lithium manganate cathode material provided by the invention, comprising:
Step 1, presoma is prepared in the synthesis of liquid phase temperature differential method: manganese source compound and aluminium salt are configured the aqueous solution of 0.2mol/L ~ 0.5mol/L by the mol ratio of 39:1 ~ 9:1, carbonate configures separately the aqueous solution of 0.2mol/L ~ 0.5mol/L, the temperature of described two groups of aqueous solution is controlled within the scope of 0 DEG C ~ 10 DEG C, rapid mixing, then be warming up to 50 DEG C ~ 80 DEG C with the speed of 10 DEG C/min, slaking 30 minutes, dry under filtering rear 40 DEG C of environment, obtain aluminium doping manganese carbonate presoma powder;
Step 2, by described aluminium doping manganese carbonate presoma powder 600 DEG C ~ 800 DEG C temperature lower calcinations 2 ~ 5 hours, obtains the spherical ions pore space structure aluminium doping oxidation manganese powder body that particle diameter is 1 μm ~ 3 μm.
Step 3, presses 1:1 ~ 1.05:1 Homogeneous phase mixing by aluminium doping oxidation manganese powder body and lithium carbonate, after being incubated 20h cooling, grinds, and repeat this roasting-grinding, until obtain particle diameter 1 ~ 2 μm of spinelle modified lithium manganate cathode material sample at 900 DEG C of temperature.
Further, described roasting-process of lapping repeats three times.
Further, described manganese source compound selects manganese sulfate.
Further, described aluminium salt compound selects aluminum nitrate.
Further, described carbonate selects sodium carbonate.
Further, described solution hybrid mode is rapid dumps.
Further, described aluminium doping oxidation manganese powder body and lithium carbonate hybrid mode are ground or ball milling.
Technical scheme of the present invention has the following advantages:
1) the modified lithium manganate material after synthesis, there is regular shape of octahedron, its lattice defect is less, and Al dopant profiles is even, be conducive to the Stability Analysis of Structures improving material, and relatively large monocrystalline primary particle also reduces the interfacial contact area between material and electrolyte, avoid Mn in charge and discharge cycles process
3+dissolve the capacity attenuation caused.
2) temperature differential method of the present invention, controls temperature field, in waters nature range, need not pressurize or adopt additive method to control to process to temperature, be convenient to synthesis and industrialization.
3) three kinds of raw material of the present invention, manganese source compound, aluminium salt compound and carbonate (especially preferred aluminum nitrate, manganese sulfate, sodium carbonate) all belong to relatively inexpensive and are easy to get.
Accompanying drawing explanation
Fig. 1 is ESEM (SEM) figure of the modified lithium manganate cathode material prepared by the embodiment of the present invention 1.
Fig. 2 is the XRD(X x ray diffraction of the modified lithium manganate cathode material prepared by the embodiment of the present invention 1) figure.
Fig. 3 is the first charge-discharge curve of the modified lithium manganate cathode material prepared by embodiments of the invention 1.
Fig. 4 is the cycle performance curve of the modified lithium manganate cathode material prepared by embodiments of the invention 1.
specific implementation method
The present invention is described in detail below in conjunction with drawings and Examples.
From background technology, LiMn
2o
4capacity fade problem constrain its large-scale application as dynamic lithium battery positive electrode.Inventor thinks through research, LiMn
2o
4mn in crystalline texture
3+because Jahn-Teller effect result in LiMn
2o
4in charge and discharge process, crystalline texture is damaged, causes the rapid decay of charge/discharge capacity thus; The approach addressed this problem is the Mn of the metal ion replacement part that other bonding forces of use are strong
3+, slow down the distortion of lattice in charge and discharge process, improve the stability of spinel structure, improve charge and discharge circulation life.
Al is conventional doped chemical, but the Uniform Doped of Al in spinel crystal becomes technologic difficult point.In conventional coprecipitation method precursor power technical process, be difficult to reach Mn and Al element being uniformly distributed in presoma.
Inventor after further research, provides a kind of preparation method of lithium ion battery modified lithium manganate cathode material in the present invention.
Embodiment 1
Step 1, presoma is prepared in the synthesis of liquid phase temperature differential method: manganese source compound and aluminium salt are configured the aqueous solution of 0.2mol/L by the mol ratio of 9:1, carbonate configures separately the aqueous solution of 0.2mol/L, the temperature of two groups of solution is controlled within the scope of 3 DEG C, rapid mixing, then be warming up to 80 DEG C of scopes with 10 DEG C/min, slaking 30 minutes, dry under filtering rear 40 DEG C of environment, obtain aluminium doping manganese carbonate presoma powder;
Step 2, by gained presoma manganese carbonate powder 700 DEG C of temperature lower calcinations 5 hours, obtains the spherical ions pore space structure aluminium doping oxidation manganese powder body that particle diameter is 1 μm ~ 3 μm.
Step 3, presses 1.02:1 Homogeneous phase mixing by aluminium doping oxidation manganese powder body and lithium carbonate, after being incubated 20h cooling, grinds, and repeats this roasting-process of lapping 3 times, obtain particle diameter 1 ~ 2 μm of spinelle modified lithium manganate cathode material sample at 900 DEG C of temperature.
As shown in Figure 1, as can be seen from the figure material has regular octahedron form to ESEM (SEM) figure of the modified lithium manganate obtained by the present embodiment, crystallinity is good, and particle size is 1 ~ 2 μm.
X-ray diffraction (XRD) figure of this modified lithium manganate as shown in Figure 2, can find out in figure that the peak type of diffraction maximum is sharp-pointed, and occur without dephasign peak.[111] d=4.747 of the diffraction maximum of crystal face, can calculate lattice constant a=8.222, than standard JCPD No.35-0732 provide 8.247 little, show after Al enters spinel structure and decrease cell volume.
The curve first of this modified lithium manganate material as shown in Figure 3, discharge and recharge is carried out with the electric current of 0.5C, first discharge specific capacity is 122mAh/g, efficiency is 96.8% first, after mixing Al, the charge and discharge process of the lithium manganate material of modification changes into homogeneous reaction, therefore shows as a continuous print sloping platform, illustrates that temperature differential method doping effectively improves the structure of lithium manganate material.
The cycle performance curve of this modified lithium manganate material as shown in Figure 4, carries out discharge and recharge with the electric current of 0.5C, and potential region is 3 ~ 4.35V, circulates after 100 times, has higher capability retention, reach 93%.
Embodiment 2
Step 1, presoma is prepared in the synthesis of liquid phase temperature differential method: manganese source compound and aluminium salt are configured the aqueous solution of 0.5mol/L by the mol ratio of 39:1, carbonate configures separately the aqueous solution of 0.5mol/L, the temperature of two groups of solution is controlled within the scope of 10 DEG C, rapid mixing, then be warming up to 80 DEG C of scopes with 10 DEG C/min, slaking 30 minutes, filter rear 40 DEG C of dryings, obtain aluminium doping manganese carbonate presoma powder;
Step 2, by gained presoma manganese carbonate powder 800 DEG C of temperature lower calcinations 2 hours, obtains the spherical ions pore space structure aluminium doping oxidation manganese powder body that particle diameter is 1 μm ~ 3 μm.
Step 3, presses 1:1 Homogeneous phase mixing by aluminium doping oxidation manganese powder body and lithium carbonate, after being incubated 20h cooling, grinds, and repeats this roasting-process of lapping 3 times, obtain particle diameter 1 ~ 2 μm of spinelle modified lithium manganate cathode material sample at 900 DEG C of temperature.
Embodiment 3
Step 1, presoma is prepared in the synthesis of liquid phase temperature differential method: manganese source compound and aluminium salt are configured the aqueous solution of 0.2mol/L by the mol ratio of 9:1, carbonate configures separately the aqueous solution of 0.2mol/L, the temperature of two groups of solution is controlled within the scope of 0 DEG C, rapid mixing, then be warming up to 50 DEG C of scopes with 10 DEG C/min, slaking 30 minutes, filter rear 40 DEG C of dryings, obtain aluminium doping manganese carbonate presoma powder;
Step 2, by gained presoma manganese carbonate powder 600 DEG C of temperature lower calcinations 2 hours, obtains the spherical ions pore space structure aluminium doping oxidation manganese powder body that particle diameter is 1 μm ~ 3 μm.
Step 3, presses 1.05:1 Homogeneous phase mixing by aluminium doping oxidation manganese powder body and lithium carbonate, after being incubated 20h cooling, grinds, and repeats this roasting-process of lapping 3 times, obtain particle diameter 1 ~ 2 μm of spinelle modified lithium manganate cathode material sample at 900 DEG C of temperature.
Embodiment 4
Step 1, presoma is prepared in the synthesis of liquid phase temperature differential method: manganese source compound and aluminium salt are configured the aqueous solution of 0.4mol/L by the mol ratio of 20:1, carbonate configures separately the aqueous solution of 0.4mol/L, the temperature of two groups of solution is controlled within the scope of 5 DEG C, rapid mixing, then be warming up to 60 DEG C of scopes with 10 DEG C/min, slaking 30 minutes, filter rear 40 DEG C of dryings, obtain aluminium doping manganese carbonate presoma powder;
Step 2, by gained presoma manganese carbonate powder 700 DEG C of temperature lower calcinations 4 hours, obtains the spherical ions pore space structure aluminium doping oxidation manganese powder body that particle diameter is 1 μm ~ 3 μm.
Step 3, presses 1.03:1 Homogeneous phase mixing by aluminium doping oxidation manganese powder body and lithium carbonate, after being incubated 20h cooling, grinds, and repeats this roasting-process of lapping 3 times, obtain particle diameter 1 ~ 2 μm of spinelle modified lithium manganate cathode material sample at 900 DEG C of temperature.
Mainly for aluminium salt hydrolysis formed aluminium hydroxide and manganese carbonate Dual system coprecipitated, the problem of even coprecipitated difficulty.Propose novel " temperature differential method ".Through obtaining lithium manganate material carries out charge-discharge test to the embodiment of the present invention, the lithium manganate material obtaining being obtained by method provided by the present invention has higher capability retention.
General, Al (OH) under normal temperature
3solubility product be 4.57 × 10
-33, and MnCO
3solubility product be 1.8 × 10
-11, therefore Al (OH)
3settling velocity be far longer than MnCO
3settling velocity, due to Al (OH) in course of reaction
3settling velocity is fast, easily generates a large amount of nucleus, forms a large amount of fine particle, and under low-temperature condition, MnCO
3nucleation rate also can accelerate, but due to two kinds precipitation moment quick-fried cores, hinder nucleus growth, particle is less.Al (OH)
3and MnCO
3owing to being the precipitation of two kinds of systems, be difficult in principle reach evenly coprecipitated effect, but the mixed process of fine particle is closer to liquid phase micro-area physical mixed, therefore break-in reaches evenly coprecipitated object.
In technical scheme of the present invention, trivalent aluminium instead of the manganese of part trivalent, the overall valence state of manganese is improved, prevent the disproportionated reaction that manganic occurs in charge and discharge process, generate divalence and tetravalent manganese ion and the structure of depositing, manganous compound is liquefied compound, therefore under the effect of electrolyte, surface reacts, can impact the cycle performance of battery, and in the positive electrode of pure manganese, because the interspersed meeting of lithium ion causes spinel structure dilation even to collapse, cause the unsteadiness of structure, after adding aluminium, certain supporting role can be played, and the coefficient of expansion reduces." temperature differential method " is the improvement be based upon on coprecipitation basis, in relative solid phase doping, the uneven of aluminium salt compound doping causes local aluminum excessive concentration etc., serve certain control action, utilize moment quick-fried nuclear control Dual system precipitating crystalline size, utilize the mode of similar liquid phase micro-area physical mixed, realize even coprecipitated object.
Although the present invention with preferred embodiment openly as above; but it is not for limiting the present invention; any those skilled in the art without departing from the spirit and scope of the present invention; the Method and Technology content of above-mentioned announcement can be utilized to make possible variation and amendment to technical solution of the present invention; therefore; every content not departing from technical solution of the present invention; the any simple modification done above embodiment according to technical spirit of the present invention, equivalent variations and modification, all belong to the protection range of technical solution of the present invention.
Claims (7)
1. a preparation method for lithium ion battery modified lithium manganate cathode material, is characterized in that, comprising:
Step 1, manganese source compound and aluminium salt are configured to the aqueous solution of 0.2mol/L ~ 0.5mol/L by the mol ratio of 39:1 ~ 9:1, carbonate configures separately the aqueous solution of 0.2mol/L ~ 0.5mol/L, the temperature of described two groups of aqueous solution is controlled within the scope of 0 DEG C ~ 10 DEG C, rapid mixing, then be warming up to 50 DEG C ~ 80 DEG C with the speed of 10 DEG C/min, slaking 30 minutes, after filtration, dry under 40 DEG C of environment, obtain aluminium doping manganese carbonate presoma powder;
Step 2, by described aluminium doping manganese carbonate presoma powder 600 DEG C ~ 800 DEG C temperature lower calcinations 2 ~ 5 hours, obtains aluminium doping oxidation manganese powder body;
Step 3, presses 1:1 ~ 1.05:1 Homogeneous phase mixing, roasting 20h at 900 DEG C by described aluminium doping oxidation manganese powder body and lithium carbonate, grinding after cooling, and repeats this roasting-process of lapping, until obtain particle diameter 1 ~ 2 μm of spinelle modified lithium manganate cathode material sample.
2. the preparation method of lithium ion battery modified lithium manganate cathode material as claimed in claim 1, it is characterized in that, described roasting-process of lapping in triplicate.
3. the preparation method of lithium ion battery modified lithium manganate cathode material as claimed in claim 1, is characterized in that, described manganese source compound selects manganese sulfate.
4. the preparation method of lithium ion battery modified lithium manganate cathode material as claimed in claim 1, is characterized in that, aluminum nitrate selected by described aluminium salt.
5. the preparation method of lithium ion battery modified lithium manganate cathode material as claimed in claim 1, is characterized in that, described carbonate selects sodium carbonate.
6. the preparation method of lithium ion battery modified lithium manganate cathode material as claimed in claim 1, it is characterized in that, described aqueous solution mode is rapid dumps.
7. the preparation method of lithium ion battery modified lithium manganate cathode material as claimed in claim 1, is characterized in that, described aluminium doping oxidation manganese powder body and lithium carbonate hybrid mode are ground or ball milling.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019041057A1 (en) | 2017-09-01 | 2019-03-07 | Universidad De Antofagasta | Manganese spinel doped with magnesium, cathode material comprising same, method for preparing same and lithium ion battery comprising same |
| CN111410233A (en) * | 2020-03-02 | 2020-07-14 | 晋江云智新材料科技有限公司 | Lithium manganese gallate serving as positive electrode material of lithium ion battery and preparation method of lithium manganese gallate |
| CN112499686A (en) * | 2020-12-18 | 2021-03-16 | 杜长福 | Method for preparing aluminum-doped battery-grade manganese oxyhydroxide by using waste manganese liquid |
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| CN101593829A (en) * | 2009-06-26 | 2009-12-02 | 湖南化工研究院 | A kind of preparation method of lithium cell anode material lithium manganate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019041057A1 (en) | 2017-09-01 | 2019-03-07 | Universidad De Antofagasta | Manganese spinel doped with magnesium, cathode material comprising same, method for preparing same and lithium ion battery comprising same |
| CN111418094A (en) * | 2017-09-01 | 2020-07-14 | 安托法加斯塔大学 | Manganese spinel doped with magnesium, cathode material comprising same, method for preparing same and lithium ion battery comprising such spinel |
| CN111410233A (en) * | 2020-03-02 | 2020-07-14 | 晋江云智新材料科技有限公司 | Lithium manganese gallate serving as positive electrode material of lithium ion battery and preparation method of lithium manganese gallate |
| CN112499686A (en) * | 2020-12-18 | 2021-03-16 | 杜长福 | Method for preparing aluminum-doped battery-grade manganese oxyhydroxide by using waste manganese liquid |
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Application publication date: 20150610 |