CN103094577A - Method for modifying ZrO2-coated lithium-rich laminar cathode material of lithium ion battery - Google Patents

Method for modifying ZrO2-coated lithium-rich laminar cathode material of lithium ion battery Download PDF

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CN103094577A
CN103094577A CN2013100180688A CN201310018068A CN103094577A CN 103094577 A CN103094577 A CN 103094577A CN 2013100180688 A CN2013100180688 A CN 2013100180688A CN 201310018068 A CN201310018068 A CN 201310018068A CN 103094577 A CN103094577 A CN 103094577A
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cathode material
rich
lithium
zro
ion battery
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赵乃勤
王志远
师春生
刘恩佐
何春年
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Tianjin University
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Tianjin University
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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
    • 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 method for modifying a ZrO2-coated lithium-rich laminar cathode material of a lithium ion battery. The method comprises the steps as follows: dissolving zirconium isopropoxide, zirconium propoxide or tetrabutyl zirconate in a solvent to prepare 0.001-1 mol/L of zirconate solution; dispersing the lithium-rich laminar cathode material in the prepared zirconate solution according to the mass ratio of ZrO2 to the lithium-rich laminar cathode material, ultrasonically mixing, sealing and stirring to obtain sol; evaporating the solvent of the prepared sol to dryness and drying to obtain a solid matter; and sintering the obtained solid matter for 1-10 h at the temperature of 350-600 DEG C to prepare the ZrO2-coated lithium-rich laminar cathode material. The ZrO2-coated lithium-rich laminar cathode material prepared with the method has the characteristics of high electrochemical capacity, good cycle stability, excellent rate performance and the like; and the preparation method is simple, easy, low in cost and good in reproducibility.

Description

ZrO 2The method of modifying of the rich lithium layered cathode material of coated lithium ion battery
Technical field
The present invention relates to a kind of ZrO 2The method of modifying of the rich lithium layered cathode material of coated lithium ion battery belongs to the anode material for lithium-ion batteries technology.
Background technology
To have energy density high because of it for lithium ion battery, and operating voltage is high, and quality is light, and volume is little, memory-less effect, advantages of environment protection and being used widely.Lithium ion battery is the desirable portable power source of the portable sets such as mobile phone, notebook, digital camera at present, utilize simultaneously " layer-built battery structure ", then a plurality of batteries are made very thin layer stacks, reach very high energy with very little volume, meet electric automobile to the requirement of accumulation power supply high-energy-density.In addition, lithium ion battery is also brought into schedule gradually in the application and development in the fields such as space satellite, weaponry and various energy storage devices.
Novel rich lithium layered cathode material xLi 2MnO 3(1-x) LiMO 2(M=Ni, Co, Mn, Ni 0.5Mn 0.5, Ni 1/3Co 1/3Mn 1/3Deng) have the large characteristics of height ratio capacity, Stability Analysis of Structures, high rate performance and cycle performance improvement space, estimating has good application prospect at electric automobile and extensive energy storage field, has therefore obtained broad research.
Although rich lithium layered cathode material have when being charged to 4.8V higher discharge capacity (〉=250mAh/g), electrolyte can be oxidized under high voltage, generation H +, improved the acidity of electrolyte, thereby made the electrode material surface film suffer the destruction of HF, have a strong impact on chemical property and the cyclical stability of material.Simultaneously, in the initial charge process, part Li +With Li 2The form of O is deviate from, and but can not again embed in discharge process, thereby produce larger irreversible capacity, simultaneously Li 2The surface of deviating from meeting destruction electrode of O causes the impedance of battery to increase, and worsens the cycle performance of battery.And the oxide surface coating is to improve one of effective ways of material electrochemical performance.(Angew. Chem. 2001,113, Nr. 18, Journal of The Electrochemical Society, 150 (12) A1723-A1725 (2003)) such as Jaephil Cho adopt ZrO 2, Al 2O 3, TiO 2, B 2O 3, SiO 2Coat LiCoO 2Positive electrode has significantly improved the chemical property of this material under high voltage 4.4V and 4.8V.CN2009100085461.2 adopts MnO 2Lithium-rich anode material is coated, and under 100 mA/g current densities, the specific discharge capacity of material has been brought up to 190mAh/g by 175mAh/g, and the cycle performance of material and high rate performance make moderate progress; (Journal of Power Sources 188 (2009) 564 – 569) such as Youyuan Huang etc. (Journal of Power Sources 188 (2009) 538 – 545) and Shao-Kang Hu etc. have prepared ZrO 2Coat Li (Ni 1/3Co 1/3Mn 1/3) O 2Positive electrode passes through ZrO 2Coating significantly improved chemical property, the especially cyclical stability of this positive electrode.In sum, oxide coats the chemical property that can obviously improve electrode material, wherein ZrO 2Coating can avoid positive electrode active materials to contact with the direct of electrolyte, effectively suppress the increase of battery impedance in charge and discharge process, the raising of electrode material cyclical stability is had great role.
Summary of the invention
The present invention aims to provide a kind of ZrO 2The method of modifying of the rich lithium layered cathode material of coated lithium ion battery, the method process is simple, and controllability is good.The rich lithium layered cathode material of the lithium ion battery that coats has good chemical property.
The present invention is realized by the following technical programs, a kind of ZrO 2The method of modifying of the rich lithium layered cathode material of coated lithium ion battery, the rich lithium layered cathode material of described lithium ion battery molecular formula is xLi 2MnO 3(1-x) LiMO 2, wherein M is Ni, Co, Mn, Ni 0.5Mn 0.5Or Ni 1/3Co 1/3Mn 1/3X is 0.1 ~ 0.9, it is characterized in that comprising following process:
1) zirconium iso-propoxide, zirconium-n-propylate or tetrabutyl zirconate are dissolved in absolute ethyl alcohol, methyl alcohol, isopropyl alcohol, normal propyl alcohol, butanols and ethylene glycol a kind of solvent wherein, be mixed with 0.001 ~ 1mol/L zirconium salt solution, stir 10min ~ 60min, the zirconium salt solution that must mix under the sealing room temperature;
2) according to ZrO 2With the mass ratio of rich lithium layered cathode material be (0.01 ~ 0.1): 1, rich lithium layered cathode material is dispersed in ultrasonic 10min ~ 60min in the zirconium salt solution of step 1) preparation, fully mix, then stir 1h ~ 5h in the room temperature lower seal, then continue to stir 1 ~ 5h and get colloidal sol;
3) with step 2) colloidal sol of system is in temperature 50 C ~ 100 ℃ solvent evaporated, and at 80 ℃ ~ 120 ℃ of temperature dry 6 ~ 24h, get solids;
4) step 3) gained solids is added sintering furnace, rise to 350 ℃ ~ 600 ℃ of temperature with 1 ℃/min ~ 10 ℃/min heating rate, constant temperature sintering 1h ~ 10h cools to room temperature with the furnace, grinds, and makes ZrO 2The rich lithium layered cathode material of coated lithium ion battery.
The invention has the advantages that: the ZrO for preparing by the method 2The lithium-rich anode material that coats is characterized in that nanometer ZrO 2Coating thickness is 5nm ~ 50nm, is porous membrane structure; The material phase analysis result shows, the rich lithium stratiform experiment material after coating all shows good layer structure, higher cation sequential 2 D degree and less cation mixing degree.This ZrO 2The lithium-rich anode material that coats has less membrane impedance and charge transfer impedance, embodies higher first discharge specific capacity and good cycle performance.The present invention can obtain the good lithium-rich anode material of chemical property, comprises first charge-discharge efficiency, high rate performance and cycle performance etc., and have the characteristics such as simple to operate, with low cost, environmental friendliness and favorable reproducibility, be fit to large-scale production.
Description of drawings
Fig. 1 is that embodiment 1 gained does not coat Li 1.2Mn 0.54Ni 0.13Co 0.13O 2SEM figure.
Fig. 2 is embodiment 1 gained ZrO 2The Li that coats 1.2Mn 0.54Ni 0.13Co 0.13O 2SEM figure.
Fig. 3 is embodiment 2 gained ZrO 2The Li that coats 1.2Mn 0.54Ni 0.13Co 0.13O 2SEM figure.
Fig. 4 is embodiment 3 gained ZrO 2The Li that coats 1.2Mn 0.54Ni 0.13Co 0.13O 2SEM figure.
Fig. 5 is that embodiment 1 does not coat and 1wt% ZrO 2Coat Li 1.2Mn 0.54Ni 0.13Co 0.13O 2XRD figure.
Fig. 6 is embodiment 1 gained ZrO 2The Li that coats 1.2Mn 0.54Ni 0.13Co 0.13O 2TEM figure.
Fig. 7 is embodiment 2 gained ZrO 2The Li that coats 1.2Mn 0.54Ni 0.13Co 0.13O 2TEM figure.
Fig. 8 is that embodiment 1 does not coat and 1wt% ZrO 2Coat Li 1.2Mn 0.54Ni 0.13Co 0.13O 2The first charge-discharge curve.
Fig. 9 is that embodiment 1 does not coat and 1wt% ZrO 2Coat Li 1.2Mn 0.54Ni 0.13Co 0.13O 2The cycle performance curve.
Figure 10 is that embodiment 1 does not coat and 1wt% ZrO 2Coat Li 1.2Mn 0.54Ni 0.13Co 0.13O 2Electrochemical impedance figure.
Embodiment
The invention will be further described below in conjunction with embodiment, and these embodiment just are used for explanation the present invention, do not limit the present invention.
Embodiment one
1) lithium-rich anode material Li 1.2Mn 0.54Ni 0.13Co 0.13O 2Preparation: with NiSO 46H 2O, CoSO 47H 2O, MnCl 24H 2O is raw material, takes nickelous sulfate 2.623kg in ratio in molecular formula, and cobaltous sulfate 2.805kg and manganese chloride 7.99kg are made into the 30L solution A that metallic element concentration is 2mol/L.Take Na 2CO 36.372kg be mixed with 1.5mol/L solution 40L, wherein add ammoniacal liquor 510.9g, mix and be designated as solution B.Add the 20L deionized water as end liquid in reactor, adopt the 30ml/min charging rate slowly to join in reactor simultaneously solution A and B, the pH value of controlling course of reaction by adjusting is 8, temperature 60 C, mixing speed 500 turn/min, rear ageing 2h reacts completely, suction filtration, washing, drying obtains nickel cobalt manganese carbonate precursor.Precursor powder is converted into oxide at 550 ℃ of sintering 6h with carbonate.Get oxide precursor 35g, take 25.232g Li 2CO 3Evenly mix with presoma.The lower 900 ℃ of lower sintering 12h of air atmosphere, programming rate is controlled at 5 ℃/min, then cools to room temperature with the furnace, prepares lithium-rich anode material Li 1.2Mn 0.54Ni 0.13Co 0.13O 2
2) drip 0.1139g Zr (OC at 40ml normal propyl alcohol solution 3H 7) 4In, cover rapidly preservative film, stirring at room 15min.After 15min, the Li that adds step 1) to make in this solution rapidly 1.2Mn 0.54Ni 0.13Co 0.13O 22.97g positive electrode covers preservative film, stirs 4h under room temperature; Must prick some apertures after stirring 3h on preservative film.
3) with step 2) solution that obtains transfers to 80 ℃ of waters bath with thermostatic control, takes off preservative film after 30min, stir until the normal propyl alcohol evaporate to dryness.
4) step 3) gained experiment material is placed in surface plate dry 12h under 80 ℃, drying box.
5) step 4) gained experiment material is heat-treated, and rises to 450 ℃ with 2 ℃/min, at 450 ℃ of sintering 4h, cools to room temperature with the furnace, makes 1wt% ZrO 2The Li that coats 1.2Mn 0.54Ni 0.13Co 0.13O 2The rich lithium layered cathode material of lithium ion battery.
Testing result:
Coating layer ZrO 2Particle is tiny, is loose spot distribution, and very large space is arranged between particle.The diffraction maximum of the positive electrode that coats is α-NaFeO 2The characteristic peak of stratiform configuration, the R-3m space group, basically identical with the XRD collection of illustrative plates that coats front sample, there is no ZrO 2Characteristic peak.
Embodiment two
1), preparation lithium-rich anode material Li 1.2Mn 0.54Ni 0.13Co 0.13O 2, step is with embodiment one step 1).
2), drip 0.2279g Zr (OC in 40ml normal propyl alcohol solution 3H 7) 4, cover rapidly preservative film, stirring at room 15min.After 15min, add rapidly 2.94g Li in mentioned solution 1.2Mn 0.54Ni 0.13Co 0.13O 2Positive electrode covers preservative film, stirs 4h under room temperature; Must prick some apertures after stirring 3h on preservative film.
3), with step 2) solution that obtains transfers to 80 ℃ of waters bath with thermostatic control, takes off preservative film after 30min, stir until the normal propyl alcohol evaporate to dryness.
4), step 3) gained experiment material is placed in surface plate dry 12h under 80 ℃, drying box.
5), step 4) gained experiment material heat-treats, and rises to 450 ℃ with 2 ℃/min, at 450 ℃ of sintering 4h, cools to room temperature with the furnace, makes 2wt% ZrO 2The Li that coats 1.2Mn 0.54Ni 0.13Co 0.13O 2Experiment material.
Embodiment three
1), preparation lithium-rich anode material Li 1.2Mn 0.54Ni 0.13Co 0.13O 2, step is with embodiment one step 1).
2), drip 0.5997g Zr (OC in 40ml normal propyl alcohol solution 3H 7) 4, cover rapidly preservative film, stirring at room 15min.After 15min, add rapidly the 2.91g positive electrode in mentioned solution, cover preservative film, stir 4h under room temperature; Must prick some apertures after stirring 3h on preservative film.
3), with step 2) solution that obtains transfers to 80 ℃ of waters bath with thermostatic control, takes off preservative film after 30min, stir until the normal propyl alcohol evaporate to dryness.
4), step 3) gained experiment material is placed in surface plate dries at drying box, temperature is 80 ℃.
5), step 4) gained experiment material heat-treats, and rises to 450 ℃ with 2～3 ℃/min, at 450 ℃ of sintering 4h, cools to room temperature with the furnace, makes 5wt% ZrO 2The Li that coats 1.2Mn 0.54Ni 0.13Co 0.13O 2Experiment material.
Embodiment four
1), preparation lithium-rich anode material Li 1.2Mn 0.6Ni 0.2O 2: with NiSO 46H 2O, MnCl 24H 2O is that raw material takes nickelous sulfate 3.974kg in the molecular formula ratio, and manganese chloride 8.978kg is made into the solution A that metallic element concentration is 2mol/L,, preparation 1.5mol/L takes Na 2CO 36.372kg be mixed with 40L solution, wherein add ammoniacal liquor 510.9g, mix and be designated as solution B.Add the 20L deionized water as end liquid in reactor, adopt the 30ml/min charging rate slowly to join in reactor simultaneously solution A and B, the pH value of controlling course of reaction by adjusting is 8, temperature 60 C, mixing speed 500 turn/min, rear ageing 2h reacts completely, suction filtration, washing, drying obtains nickel cobalt manganese carbonate precursor.Precursor powder is converted into oxide at 550 ℃ of sintering 6h with carbonate.Get oxide precursor 35g, take 25.232g Li 2CO 3Evenly mix with presoma.The lower 900 ℃ of lower sintering 12h of air atmosphere, programming rate is controlled at 5 ℃/min, then cools to room temperature with the furnace, prepares lithium-rich anode material Li 1.2Mn 0.6Ni 0.2O 2
2), drip 0.1139g Zr (OC in 40ml normal propyl alcohol solution 3H 7) 4, cover rapidly preservative film, stirring at room 15min.After 15min, add rapidly 2.97g Li in mentioned solution 1.2Mn 0.6Ni 0.2O 2Positive electrode covers preservative film, stirs 4h under room temperature; Must prick some apertures after stirring 3h on preservative film.
3), with step 2) solution that obtains transfers to 80 ℃ of waters bath with thermostatic control, takes off preservative film after 30min, stir until the normal propyl alcohol evaporate to dryness.
4), step 3) gained experiment material is placed in surface plate dry 12h under 80 ℃, drying box.
5), step 4) gained experiment material heat-treats, and rises to 450 ℃ with 2 ℃/min, at 450 ℃ of sintering 4h, cools to room temperature with the furnace, makes 1wt% ZrO 2The Li that coats 1.2Mn 0.6Ni 0.2O 2Experiment material.
Embodiment five
1), preparation lithium-rich anode material Li 1.2Mn 0.6Ni 0.2O 2, step is with embodiment four step 1).
2), drip 0.2279g Zr (OC in 40ml normal propyl alcohol solution 3H 7) 4, cover rapidly preservative film, stirring at room 15min.After 15min, add rapidly the 2.94g positive electrode in mentioned solution, cover preservative film, stir 4h under room temperature; Must prick some apertures after stirring 3h on preservative film.
3), with step 2) solution that obtains transfers to 80 ℃ of waters bath with thermostatic control, takes off preservative film after 30min, stir until the normal propyl alcohol evaporate to dryness.
4), step 3) gained experiment material is placed in surface plate dry 12h under 80 ℃, drying box.
5), step 4) gained experiment material heat-treats, and rises to 450 ℃ with 2 ℃/min, at 450 ℃ of sintering 4h, cools to room temperature with the furnace, makes 2wt% ZrO 2The Li that coats 1.2Mn 0.6Ni 0.2O 2Experiment material.
Embodiment six
1), preparation lithium-rich anode material Li 1.2Mn 0.6Ni 0.2O 2, step is with embodiment four step 1).
2), drip 0.5997g Zr (OC in 40ml normal propyl alcohol solution 3H 7) 4, cover rapidly preservative film, stirring at room 15min.After 15min, add rapidly the 2.91g positive electrode in mentioned solution, cover preservative film, stir 4h under room temperature; Must prick some apertures after stirring 3h on preservative film.
3), with step 2) solution that obtains transfers to 80 ℃ of waters bath with thermostatic control, takes off preservative film after 30min, stir until the normal propyl alcohol evaporate to dryness.
4), step 3) gained experiment material is placed in surface plate dry 12h under 80 ℃, drying box.
5), step 4) gained experiment material heat-treats, and rises to 450 ℃ with 2 ℃/min, at 450 ℃ of sintering 4h, cools to room temperature with the furnace, makes 1wt% ZrO 2The Li that coats 1.2Mn 0.6Ni 0.2O 2Experiment material.

Claims (1)

1. ZrO 2The method of modifying of the rich lithium layered cathode material of coated lithium ion battery, the rich lithium layered cathode material of described lithium ion battery molecular formula is xLi 2MnO 3(1-x) LiMO 2, wherein M is Ni, Co, Mn, Ni 0.5Mn 0.5Or Ni 1/3Co 1/3Mn 1/3X is 0.1 ~ 0.9, it is characterized in that comprising following process:
1) zirconium iso-propoxide, zirconium-n-propylate or tetrabutyl zirconate are dissolved in absolute ethyl alcohol, methyl alcohol, isopropyl alcohol, normal propyl alcohol, butanols and ethylene glycol a kind of solvent wherein, be mixed with 0.001 ~ 1mol/L zirconium salt solution, stir 10min ~ 60min, the zirconium salt solution that must mix under the sealing room temperature;
2) according to ZrO 2With the mass ratio of rich lithium layered cathode material be (0.01 ~ 0.1): 1, rich lithium layered cathode material is dispersed in ultrasonic 10min ~ 60min in the zirconium salt solution of step 1) preparation, fully mix, then stir 1h ~ 5h in the room temperature lower seal, then continue to stir 1 ~ 5h and get colloidal sol;
3) with step 2) colloidal sol of system is in temperature 50 C ~ 100 ℃ solvent evaporated, and at 80 ℃ ~ 120 ℃ of temperature dry 6 ~ 24h, get solids;
4) step 3) gained solids is added sintering furnace, rise to 350 ℃ ~ 600 ℃ of temperature with 1 ℃/min ~ 10 ℃/min heating rate, constant temperature sintering 1h ~ 10h cools to room temperature with the furnace, grinds, and makes ZrO 2The rich lithium layered cathode material of coated lithium ion battery.
CN2013100180688A 2013-01-18 2013-01-18 Method for modifying ZrO2-coated lithium-rich laminar cathode material of lithium ion battery Pending CN103094577A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103474637A (en) * 2013-08-30 2013-12-25 厦门钨业股份有限公司 Lithium ion battery anode material and preparation method thereof
CN104617286A (en) * 2015-01-18 2015-05-13 北京工业大学 Simple surface modification method of Li-rich cathode material
CN106784677A (en) * 2016-12-16 2017-05-31 江南大学 A kind of preparation of lithium-enriched cathodic material of lithium ion battery and improved method
CN108889941A (en) * 2018-08-01 2018-11-27 中铁四局集团第二工程有限公司 A method of zirconium oxide is coated on tungsten carbide-cobalt composite powder body surface
CN108987734A (en) * 2018-09-11 2018-12-11 山东玉皇新能源科技有限公司 Stratiform lithium-rich anode material of manganese dioxide cladding and preparation method thereof and lithium ion battery obtained

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CN1556551A (en) * 2003-12-30 2004-12-22 中国科学院上海微系统与信息技术研究 Surface covering material of lithium ion battery positive electrode and its technology
CN101409342A (en) * 2008-10-31 2009-04-15 深圳市贝特瑞新能源材料股份有限公司 Method for preparing composite anode material
CN101562245A (en) * 2009-05-22 2009-10-21 北京工业大学 Method for modifying high-rate lithium-rich anode material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1556551A (en) * 2003-12-30 2004-12-22 中国科学院上海微系统与信息技术研究 Surface covering material of lithium ion battery positive electrode and its technology
CN101409342A (en) * 2008-10-31 2009-04-15 深圳市贝特瑞新能源材料股份有限公司 Method for preparing composite anode material
CN101562245A (en) * 2009-05-22 2009-10-21 北京工业大学 Method for modifying high-rate lithium-rich anode material

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103474637A (en) * 2013-08-30 2013-12-25 厦门钨业股份有限公司 Lithium ion battery anode material and preparation method thereof
WO2015027765A1 (en) * 2013-08-30 2015-03-05 Xiamen Tungsten Co., Ltd Cathode material of lithium-ion battery and method for making the same
CN104617286A (en) * 2015-01-18 2015-05-13 北京工业大学 Simple surface modification method of Li-rich cathode material
CN106784677A (en) * 2016-12-16 2017-05-31 江南大学 A kind of preparation of lithium-enriched cathodic material of lithium ion battery and improved method
CN108889941A (en) * 2018-08-01 2018-11-27 中铁四局集团第二工程有限公司 A method of zirconium oxide is coated on tungsten carbide-cobalt composite powder body surface
CN108889941B (en) * 2018-08-01 2020-10-27 中铁四局集团第二工程有限公司 Method for coating zirconium oxide on surface of tungsten carbide-cobalt composite powder
CN108987734A (en) * 2018-09-11 2018-12-11 山东玉皇新能源科技有限公司 Stratiform lithium-rich anode material of manganese dioxide cladding and preparation method thereof and lithium ion battery obtained

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Application publication date: 20130508