CN105789558A - High-rate capability lithium-rich manganese-based cathode material for lithium-ion battery and preparation method of high-rate capability lithium-rich manganese-based cathode material - Google Patents
High-rate capability lithium-rich manganese-based cathode material for lithium-ion battery and preparation method of high-rate capability lithium-rich manganese-based cathode material Download PDFInfo
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Abstract
The invention discloses a high-rate capability lithium-rich manganese-based cathode material for a lithium-ion battery and a preparation method of the high-rate capability lithium-rich manganese-based cathode material. The chemical formula of the material is Li[LixNiaCobMncAd]O2, wherein A is at least two of Zr, Na and K and comprises Zr; x, a, b, c and d represent the atomic ratios; x+a+b+c+d=1; x is smaller than or equal to 0.3 and greater than 0.1; a is smaller than or equal to 0.3 and greater than 0.1; b is smaller than or equal to 0.3 and greater than or equal to 0.1; c is smaller than or equal to 0.6 and greater than 0.4; and d is smaller than or equal to 0.1 and greater than 0.002. The preparation method comprises the following steps: with lithium carbonate, manganese carbonate, cobaltosic oxide, nickel protoxide, oxide of A or carbonate as raw materials, weighing corresponding raw materials at the stoichiometric ratio in the chemical formula; mixing the raw materials and pre-grinding and dispersing the mixture with a certain amount of deionized water; transferring the pre-ground slurry into a sand mill and further carrying out ultrafine grinding for 1-8 hours; carrying out spray drying treatment on the obtained slurry; and roasting the obtained dry powder in an air atmosphere of 500-1,000 DEG C, carrying out heat preservation for 10-40 hours and cooling the product to a room temperature in a furnace. A proper amount of zirconium, sodium and potassium are added to the Li[LixNiaCobMnc]O2 layered composite structure material, so that the rate capability and the like of the material are obviously improved.
Description
Technical field
The present invention relates to anode material for lithium ion battery, be specifically related to a kind of lithium-rich manganese-based anode material for lithium-ion batteries of high rate capability and preparation method thereof, belong to anode material for lithium-ion batteries technical field.
Background technology
The life of people is just produced increasingly deep effect by lithium ion battery, is increasingly applied in modern society, not only in the portable electronics such as mobile phone, notebook computer, also has extraordinary application prospect in electric automobile field.The requirement of lithium ion battery is also being improved constantly by people, especially electric automobile in the urgent need to high security, high-energy-density, high power, Large Copacity, the long-life, high-environmental, low cost lithium ion battery.
The rich lithium manganese base solid solution material Li of layer structure2MnO3-LiMO2(M=Ni, Co, Mn) is owing to having specific capacity height (more than 200mAh/g), Heat stability is good, cheap and become the focus of Recent study.Although rich lithium solid-solution material has a significantly high specific capacity, but its practical application still suffers from the problems such as circulation irreversible capacity high (up to 40-100mAh/g), high rate performance first be poor.
In recent years, in order to improve coulombic efficiency first and the multiplying power discharging property of lithium-rich manganese base material, the technology currently mainly adopted is Surface coating, the side reaction of the release of oxygen, minimizing and electrolyte is suppressed by Surface coating, increase the electric conductivity on surface, thus improving the rich problem that lithium material coulombic efficiency is low, high rate performance is poor simultaneously.Element doping correlational study is less, several patent is had once to relate to the doping in rich lithium solid solution such as the element that includes zirconium, but all only broadly mentioning the elements such as Zr can partly substitute host element, such as patent documentation US7358009, US20090220859A1, CN102484249A, but all do not have the related embodiment provided containing zirconium sample, also without correlated performance data.
Summary of the invention
Based on this, it is an object of the invention to provide a kind of lithium-rich manganese-based anode material for lithium-ion batteries, this positive electrode has high specific capacity first, coulombic efficiency and high rate performance.
Another object of the present invention is to the preparation method that a kind of described lithium-rich manganese-based anode material for lithium-ion batteries is provided.
For achieving the above object, the present invention is by the following technical solutions:
A kind of lithium-rich manganese-based anode material for lithium-ion batteries of high rate capability, the chemical formula of this material is: Li [LixNiaCobMncAd]O2, wherein: A is at least two in Zr, Na, K, and Zr must be contained；X, a, b, c, d represent atomic ratio, x+a+b+c+d=1,0.1 < x≤0.3,0.1 < a≤0.3,0.1≤b≤0.3,0.4 < c≤0.6,0.002 < d≤0.1.
The microstructure of this positive electrode is Li2MnO3And LiMO2Layered composite structure, wherein, M is Ni, Co, Mn and A.
Preferably, 0.1 < x≤0.2 in the chemical formula of this material, 0.2 < b≤0.3,0.1 < b≤0.2,0.4 < c≤0.55,0.002 < d≤0.05.
Preferably, 0.1 < x≤0.2 in the chemical formula of this material, 0.2≤a≤0.3,0.1≤b≤0.2,0.5≤c≤0.6,0.002 < d≤0.05.
The preparation method of described anode material for lithium-ion batteries, including at least following 5 steps:
(1) respectively with lithium carbonate, manganese carbonate, Cobalto-cobaltic oxide, nickel protoxide, the oxide of A or carbonate for raw material, according to chemical formula Li [LixNiaCobMncAd]O2Metering ratio weigh corresponding raw material；
(2) being mixed by the raw material of step (1), be equipped with a certain amount of deionized water, pre-grinding disperses；
(3) slurry after step (2) pre-grinding is proceeded to the further Ultrafine Grinding 1-8h of sand mill, obtain slurry；
(4) slurry obtained through step (3) is carried out spray drying treatment；
(5) dried powder of step (4) gained is carried out under 500-1000 DEG C of air atmosphere roasting, be incubated 10-40h, cool to room temperature with the furnace.
Wherein, the median particle diameter D of granule in described step (3) Ultrafine Grinding disposed slurry50Less than 0.5 μm, it is preferred that median particle diameter D50Less than 0.3 μm, preferred median particle diameter D50Less than 0.2 μm.
In described step (5), the temperature of roasting is preferably 700-900 DEG C.
The positive electrode of the present invention is mixed with conductive carbon and bonding agent, dissolves and form anode sizing agent in organic solvent, and the anode sizing agent obtained is coated in the positive pole forming lithium ion battery on support conducting base.Anode compatible to the positive pole of formation and electricity, barrier film, electrolyte are placed in container and form lithium ion battery.
It is an advantage of the current invention that:
The present invention is at Li [LixNiaCobMnc]O2Adding appropriate zirconium, sodium, potassium in layered composite structure material, the addition of these elements improves Lithium-ion embeding/deviate from speed, reduces Charge-transfer resistance, so that the high rate performance etc. of this material obtains and improves significantly.
Accompanying drawing explanation
Fig. 1-2 is scanning electron microscope (SEM) photo of the positive electrode prepared by embodiment 1.
Fig. 3 is the X ray diffracting spectrum (XRD) of the positive electrode prepared by embodiment 3.
The first charge-discharge comparison diagram of the battery that the positive electrode that Fig. 4 is embodiment 3 and prepared by comparative example assembles.
The high rate performance comparison diagram of the battery that the positive electrode that Fig. 5 is embodiment 3 and prepared by comparative example assembles.
Detailed description of the invention
Below according to drawings and Examples, the present invention will be further described, but embodiments of the present invention are not limited to this.
Comparative example
By chemical formula Li1.2Ni0.13Co0.13Mn0.54O2In each metallic element mol ratio weigh the MnCO that gross mass is 200g3、NiO、Co3O4、Li2CO3Mixed-powder, with deionized water for disperse medium, grinds 2h in agitating ball mill, is then transferred to afterwards in sand mill, grinds 4h；The slurry obtained is carried out spray drying treatment, obtains spray-dried powders；Take the 10g roasting in Muffle furnace of this powder: be warming up to 900 DEG C of roasting 12h, cool to room temperature with the furnace, obtain the lithium-rich positive electrode without zirconium.
Embodiment 1
By chemical formula Li1.2Co0.13Ni0.13Mn0.53Zr0.05Na0.05O2In each metallic element mol ratio weigh the MnCO of gross mass 200g3、NiO、Co3O4、Li2CO3、ZrO2、Na2CO3Mixed-powder, grinds thereafter, spray drying and the same comparative example of roasting technique.
Embodiment 2-7
Raw material and the preparation technology of embodiment 2-7 are as shown in the table, and except the process conditions of following table, other process conditions are all identical with embodiment 1.
Fig. 1-2 is the scanning electron microscopic picture of the positive electrode prepared by embodiment 1, can be seen that from scanning electron microscopic picture, this material microscopic pattern be piled into spherical second particle by primary particle, porous surface, such structure is conducive to the immersion of electrolyte, the particle diameter of its primary particle mostly is 50-200nm, mean diameter < 150nm.
Fig. 3 is the X ray diffracting spectrum (XRD) of the positive electrode prepared by example 3.(the XRD figure spectrum of material prepared by all the other embodiments is similar, omits).It can be seen that the sample of fired process, it is obtained for stratiform α-NaFeO2Layer structure, 2 θ are at 20～25 ° of superlattice structures occurring in that solid-solution material possesses, and the division of (018) and (110) peak is substantially.Do not find the peak relevant to zirconium and sodium element, illustrate in the lattice that zirconium and sodium element enter material.
Prepared by positive pole
Using the material of embodiment 3 preparation as active substance, with conductive agent (SP), binding agent (PVDF) according to 8∶1∶The proportioning of 1 weighs, and first active substance and conductive agent is dry mixed 4h, is dissolved in by PVDF in N-N dimethylformamide, then the conductive agent of the active substance mixed is added wherein, stir, form anode sizing agent, anode sizing agent is coated on aluminium foil, dries in drying baker.
Prepared by testing of materials half-cell
The electrode cutting dried being become 1 × 1cm, then roll-in, dry at vacuum drying oven, as the positive pole of battery, the negative pole of battery adopts lithium metal, and the composition of electrolyte is mainly the LiPF of 1M6And DMC/EC/DEC (1: 1: 1), positive pole, negative pole and electrolyte are placed in container and form test battery.
The electrochemical property test of material
By the test battery of composition, it is 20mAg in electric current density-1(0.1C), charging/discharging voltage scope 4.8～2V, the charge-discharge property of test battery.The high rate performance of battery is tested under 0.1C, 0.2C, 0.5C, 1C, 2C, 3C multiplying power.
The preparation of lithium ion battery
The material of embodiment 3 preparation is as positive electrode, and native graphite, as negative pole, selects the PP/PE/PP of three layers as barrier film, and the composition of electrolyte is mainly the LiPF of 1M6And DMC/EC/DEC (1: 1: 1), make Soft Roll laminated lithium ion battery.
Battery performance test
The lithium ion battery that will make, at 0.2C, voltage is the energy density testing battery under 4.25V～3V.
Positive electrode prepared by embodiment 1-7, assembles lithium ion battery, is 4.8～2.0V in voltage range, and the discharge performance tables of data under different multiplying is as shown in the table.
The first charge-discharge comparison diagram of the battery that the positive electrode that Fig. 4 is embodiment 3 and prepared by comparative example assembles.It can be seen that within the scope of the blanking voltage of 2～4.8V, the initial charge specific capacity of embodiment 3 is 341mAhg-1, specific discharge capacity is 293mAhg-1, coulombic efficiency is 85.9%；And the initial charge specific capacity of comparative example is 341mAhg-1, specific discharge capacity is 256mAhg-1, coulombic efficiency is 75.1%.Visible, discharge capacity first and the coulombic efficiency of material prepared by employing the inventive method are superior to comparative example.
The high rate performance comparison diagram of the lithium ion battery that the positive electrode that Fig. 5 is embodiment 3 and prepared by comparative example assembles.The positive electrode of embodiment 3 preparation, assembles lithium ion battery, and battery is 293mAhg at the specific discharge capacity of 0.1C-1, the specific discharge capacity of 1C is 242mAhg-1, the specific discharge capacity of 3C is 209mAhg-1.And positive electrode prepared by comparative example, assembling lithium ion battery, battery is 255mAhg at the specific discharge capacity of 0.1C-1, the specific discharge capacity of 1C is 198mAhg-1, the specific discharge capacity of 3C is 163mAhg-1.Data show, the positive electrode high rate performance of embodiment 3 preparation is apparently higher than comparative example.
Utilizing active substance prepared by embodiment 3 as the positive electrode of battery, the energy density of the lithium ion battery assembled with reference to above-mentioned method is 260Whkg-1。
In conjunction with above-mentioned data, the first discharge specific capacity of the material prepared by the present invention, first efficiency and high rate performance all get a promotion significantly, the performance of material has also reached the requirement of electrokinetic cell, and simple to operate, preparation cost is low, it is possible to be applied in commercial production.
Claims (10)
1. the lithium-rich manganese-based anode material for lithium-ion batteries of high rate capability, it is characterised in that the chemical formula of this material is: Li [LixNiaCobMncAd]O2, wherein: A is at least two in Zr, Na, K, and Zr must be contained；X, a, b, c, d represent atomic ratio, x+a+b+c+d=1,0.1 < x≤0.3,0.1 < a≤0.3,0.1≤b≤0.3,0.4 < c≤0.6,0.002 < d≤0.1.
2. the lithium-rich manganese-based anode material for lithium-ion batteries of high rate capability according to claim 1, it is characterised in that its microstructure is Li2MnO3And LiMO2Layered composite structure, wherein, M is Ni, Co, Mn and A.
3. the lithium-rich manganese-based anode material for lithium-ion batteries of high rate capability according to claim 1 and 2, it is characterized in that, 0.1 < x≤0.2,0.1 < a≤0.2,0.2 < b≤0.3,0.4 < c≤0.55,0.002 < d≤0.05.
4. the lithium-rich manganese-based anode material for lithium-ion batteries of high rate capability according to claim 1 and 2, it is characterised in that and 0.1 < x≤0.2,0.2≤a≤0.3,0.1≤b≤0.2,0.5≤c≤0.6,0.002 < d≤0.05.
5. the preparation method of anode material for lithium-ion batteries according to any one of claim 1-4, it is characterised in that including at least following 5 steps:
(1) respectively with lithium carbonate, manganese carbonate, Cobalto-cobaltic oxide, nickel protoxide, the oxide of A or carbonate for raw material, chemical formula Li [Li described in claim 1xNiaCobMncAd]O2Metering ratio weigh corresponding raw material；
(2) being mixed by the raw material of step (1), be equipped with deionized water, pre-grinding disperses；
(3) slurry after step (2) pre-grinding is proceeded to the further Ultrafine Grinding 1-8h of sand mill, obtain slurry；
(4) slurry obtained through step (3) is carried out spray drying treatment；
(5) dried powder of step (4) gained is carried out under 500-1000 DEG C of air atmosphere roasting, be incubated 10-40h, cool to room temperature with the furnace.
6. preparation method according to claim 5, it is characterised in that the median particle diameter D of granule in described step (3) Ultrafine Grinding disposed slurry50Less than 0.5 μm.
7. preparation method according to claim 6, it is characterised in that granule median particle diameter D in described step (3) Ultrafine Grinding disposed slurry50Less than 0.2 μm.
8. preparation method according to claim 5, it is characterised in that in described step (5), the temperature of roasting is 700-900 DEG C.
9. the positive pole of a lithium ion battery, it is characterized in that, positive electrode as described in claim 1-4 any one is mixed with conductive carbon and bonding agent, dissolve and form anode sizing agent in organic solvent, and the anode sizing agent obtained is coated in the positive pole forming lithium ion battery on support conducting base.
10. a lithium ion battery, it is characterised in that anode compatible to the positive pole described in claim 9 and electricity, barrier film, electrolyte are placed in container and form lithium ion battery.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107204429A (en) * | 2017-06-22 | 2017-09-26 | 北方奥钛纳米技术有限公司 | The preparation method and anode material for lithium-ion batteries and lithium ion battery of nickel-cobalt-manganese ternary material |
| CN109860587A (en) * | 2019-02-28 | 2019-06-07 | 蜂巢能源科技有限公司 | Positive electrode of lithium ion battery and preparation method thereof, lithium ion battery |
| CN114538533A (en) * | 2022-01-25 | 2022-05-27 | 合肥融捷能源材料有限公司 | Nickel-cobalt lithium manganate and preparation method and application thereof |
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| CN103094550A (en) * | 2011-10-31 | 2013-05-08 | 北京有色金属研究总院 | Preparation method of lithium-rich anode material |
| CN103606663A (en) * | 2013-11-28 | 2014-02-26 | 上海空间电源研究所 | Multiplying-power lithium-rich composite anode material and preparation method thereof |
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| WO2012061191A2 (en) * | 2010-11-02 | 2012-05-10 | Envia Systems, Inc. | Lithium ion batteries with supplemental lithium |
| CN103094550A (en) * | 2011-10-31 | 2013-05-08 | 北京有色金属研究总院 | Preparation method of lithium-rich anode material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107204429A (en) * | 2017-06-22 | 2017-09-26 | 北方奥钛纳米技术有限公司 | The preparation method and anode material for lithium-ion batteries and lithium ion battery of nickel-cobalt-manganese ternary material |
| CN109860587A (en) * | 2019-02-28 | 2019-06-07 | 蜂巢能源科技有限公司 | Positive electrode of lithium ion battery and preparation method thereof, lithium ion battery |
| CN114538533A (en) * | 2022-01-25 | 2022-05-27 | 合肥融捷能源材料有限公司 | Nickel-cobalt lithium manganate and preparation method and application thereof |
| CN114538533B (en) * | 2022-01-25 | 2023-10-27 | 合肥融捷能源材料有限公司 | Nickel cobalt lithium manganate and preparation method and application thereof |
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