CN1412119A - Method for synthesizing positive material of lithium ion cell by means of organic acid complexation combustion - Google Patents

Method for synthesizing positive material of lithium ion cell by means of organic acid complexation combustion Download PDF

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Publication number
CN1412119A
CN1412119A CN02147763A CN02147763A CN1412119A CN 1412119 A CN1412119 A CN 1412119A CN 02147763 A CN02147763 A CN 02147763A CN 02147763 A CN02147763 A CN 02147763A CN 1412119 A CN1412119 A CN 1412119A
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compound
organic acid
lithium ion
positive electrode
ion cell
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CN1169724C (en
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陈文�
麦立强
徐庆
朱泉峣
周静
黄学辉
郭万里
彭俊锋
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WUHAN LIGONG LIQIANG ENERGY CO., LTD.
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Wuhan University of Technology WUT
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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

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Abstract

The method for synthesizing positive electrode material of lithium ion cell includes the following steps: preparing raw material according to the requirements for synthesizing product, ball-grinding for 3-10 hr, dissolving the above-mentioned material in deionized water, adding organic acid saturated solution whose number of carbon atoms is 2-8 while stirring to discharge lots of bubbles, using ultrasonic wave to make treatment, then heating in water bath, controlling temp. at 60-100 deg.C to obtain dried gel, ball-grinding dried gel and making combustion reaction, heat-insulating for 3 hr. at 450 deg.C in the furnace so as to obtain the invented positive electrode material.

Description

A kind of method of organic acid complexing burning synthesis of anode material of lithium-ion battery
Technical field
The present invention relates to a kind of method, belong to the lithium ion battery material technical field by organic acid complexing burning synthesis of anode material of lithium-ion battery.
Background technology
Lithium ion battery is the latest generation secondary cell that grows up the nineties in 20th century.The maximum anode material for lithium-ion batteries of research is the transition metal oxide LiCoO of three kinds of rich lithiums at present 2, LiNiO 2And LiMnO 4, their operating voltage is 4.1～4.5V.Recently find a kind of novel lithium-containing transition metal oxide positive electrode material LiMVO 4, M is Ni, Co or Cu, has inverse spinel structure, has the noble potential of 4.8V (with respect to Li owing to its positively charged ion mixedness can reach 100% +/ Li), thereby be used as lithium ion battery novel anode active material.Synthetic LiMVO 4General employing solid reaction process and hydrothermal method, but the solid state reaction required time is long, temperature is high, energy consumption is big, and product granularity and element skewness, hydrothermal method conversion unit are complicated, the difficult control of process.Adopt organic acid complexing burning synthesis of anode material of lithium-ion battery still rare.
Summary of the invention
Purpose of the present invention will provide a kind of novel method of low-cost less energy-consumption synthesis of anode material of lithium-ion battery.
The present invention seeks to realize with following technical scheme, its method steps is: 1. by the Li compound of requirement synthetic product requirement, the M compound, V compound molar ratio ingredient, M compound are to be selected from any metallic element compound among Ni, Co, the Cu or the mixture of two or more metallic element compounds in them; 2. admixtion is placed planetary mills, ball milling 3～10 hours; 3. the above-mentioned material of wearing into is dissolved in the deionized water, adds carbonatoms while stirring and be 2～8 organic acid saturated solution; 4. with 3 gained slips, be 200～600W with power, after frequency is the ultrasonication of 20～40Hz, carry out heating in water bath, temperature is controlled at 60～100 ℃, gets xerogel; 5. carry out combustion reactions behind the xerogel ball milling, and in stove 450 ℃ of following sintering, promptly get anode active material of lithium ion battery.
Described agglomerating method is: temperature rise rate is 100～200 ℃/hour, and 450 ℃ of sintering temperatures, soaking time are 3 hours.
The raw materials used common raw material that is of the present invention, equipment is simple, and synthesising reacting time is short, and sintering temperature is low, manufacturing cost is comparatively cheap, and method for making is simple, and favorable reproducibility meets environmental requirement, products therefrom crystallization degree height, granularity is little, and granularity and element are evenly distributed.
Description of drawings
Fig. 1 is the XRD figure of the embodiment of the invention 1 product.
Fig. 2 is the SEM figure of the embodiment of the invention 1.
Fig. 3 a, b are respectively the FTIR figure and the Raman figure of the embodiment of the invention 1 product.
Fig. 1 explanation: the equal and LiCoVO of the position of each diffraction peak of XRD figure of synthetic product and relative intensity 4Standard JCPDS card (38-1396) matches, and shows that product is single-phase LiCoVO 4LiMVO 4Crystalline characteristics can recently characterize this figure I with the intensity at (220) peak and (311) peak (220)/ I (311)=0.5 shows LiCoVO 4Degree of crystallinity very high.
Fig. 2 explanation: synthetic LCoVO 4Spherical in shape, the median size of primary particle is 300nm, and particle surface is smooth, although there is certain agglomeration, generally, size distribution is more even.
Fig. 3 explanation: the FTIR figure of product and Raman figure are at 820cm -1Near and 330cm -1Near LiCoVO appears respectively 4Charateristic avsorption band.Wherein FTIR figure is positioned at 820cm -1The high frequency absorption band at place is corresponding to VO 4Tetrahedron has A 1Symmetric stretching vibration, and be positioned at 335 -1The absorption band at place is then corresponding to VO 4Tetrahedron has the symmetric angle vibration of E.Raman spectrum highest peak lays respectively at 796.6cm -1And 821.7cm -1, belong to VO 4The inner mould vibration peak of the strong vibration of V-O in the tetrahedron is at 330cm -1Near the appearance belongs to VO in more weak peak 4Tetrahedral angle vibration.
Embodiment
Embodiment 1:(1) presses LiOH, Co (CH 3CH 2COO) 2, NH 4VO 3By 1: 1: 1 molar ratio ingredient; (2) admixtion is placed planetary mills, ball milling 3～10 hours; (3) above-mentioned slurry is dissolved in the deionized water, adds the saturated solution of citric acid while stirring; (4) be 400W with power, after frequency is the ultrasonication of 40Hz, carry out heating in water bath, temperature is controlled at 80 ℃, gets xerogel; (5) carry out combustion reactions behind the xerogel ball milling, and the temperature rise rate by 150 ℃/hour is warming up to 450 ℃ in retort furnace, is incubated 3 hours, can make light brown inverse spinel structure positive electrode active materials.
Analytical test shows (seeing accompanying drawing), and product is single-phase LiCoVO 4, the crystallization degree height, the product particle surface is smooth, and size distribution is even.The product element distributes comparatively even, and chemical general formula is Li 0.9671Co 0.9942VO 4
Embodiment 2～embodiment 5:
Raw material Proportioning Organic acid Temperature rise rate (℃/h)
Embodiment 2 ????Li 2CO 3+Ni 2(OH)CO 3+V 2O 5 ????LiNiVO 4 Acetate ????100
Embodiment 3 ????LiOH+Cu(CH 3CH 2COO) 2+ ????NH 4VO 3 ????LiCuVO 4 Oxalic acid ????120
Embodiment 4 ????Li 2CO 3+Ni(NO 3) 2+Co ????(CH 3CH 2COO) 2 ????LiNi 0.5Co 0.5VO 4 Acetate+citric acid ????140
Embodiment 5 ????Li 2CO 3+Ni(NO 3) 2+ ????Co(NO 3) 2+Cu(NO 3) 2 ????LiNi 0.3Co 0.3Cu 0.4VO Oxalic acid+citric acid ????160
Can obtain the inverse spinel structure positive electrode active materials of correspondence with reference to the method for embodiment 1 by above experiment parameter.

Claims (2)

1, a kind of method by organic acid complexing burning synthesis of anode material of lithium-ion battery, it is characterized in that step is: (1) is by the Li compound of institute's synthetic product requirement, the M compound, V compound molar ratio ingredient, M compound are to be selected from any metallic element compound among Ni, Co, the Cu or the mixture of two or more metallic element compounds in them; (2) admixtion is placed planetary mills, ball milling 3～10 hours; (3) the above-mentioned material of wearing into is dissolved in the deionized water, adds carbonatoms while stirring and be 2～8 organic acid saturated solution; (4) with (3) gained slip, be 200～600W with power, after frequency is the ultrasonication of 20～40Hz, carry out heating in water bath, temperature is controlled at 60～100 ℃, gets xerogel; (5) carry out combustion reactions behind the xerogel ball milling, and in stove 450 ℃ of following sintering, can make the inverse spinel structure positive electrode active materials.
2, the method for claim 1 is characterized in that described agglomerating temperature rise rate is 100～200 ℃/hour, 450 ℃ of sintering temperatures, soaking time 3 hours.
CNB021477639A 2002-11-29 2002-11-29 Method for synthesizing positive material of lithium ion cell by means of organic acid complexation combustion Expired - Fee Related CN1169724C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104900875A (en) * 2015-05-15 2015-09-09 武汉理工大学 NaCuVO4 nanoparticles and preparation method and application thereof
CN105047923A (en) * 2015-08-14 2015-11-11 东莞市迈科科技有限公司 Lithium copper vanadate anode material for lithium ion battery and preparation method of lithium copper vanadate anode material
CN107482169A (en) * 2017-07-28 2017-12-15 苏州协鑫集成储能科技有限公司 Vanadic acid cobalt lithium and its preparation method and application
CN112185642A (en) * 2020-09-23 2021-01-05 江西艾特磁材有限公司 Method for coating magnetic powder core with ball milling modified sol-gel

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104900875A (en) * 2015-05-15 2015-09-09 武汉理工大学 NaCuVO4 nanoparticles and preparation method and application thereof
CN104900875B (en) * 2015-05-15 2018-04-27 武汉理工大学 NaCuVO4Nano particle and its preparation method and application
CN105047923A (en) * 2015-08-14 2015-11-11 东莞市迈科科技有限公司 Lithium copper vanadate anode material for lithium ion battery and preparation method of lithium copper vanadate anode material
CN107482169A (en) * 2017-07-28 2017-12-15 苏州协鑫集成储能科技有限公司 Vanadic acid cobalt lithium and its preparation method and application
CN107482169B (en) * 2017-07-28 2020-06-23 苏州协鑫集成储能科技有限公司 Lithium cobalt vanadate, and preparation method and application thereof
CN112185642A (en) * 2020-09-23 2021-01-05 江西艾特磁材有限公司 Method for coating magnetic powder core with ball milling modified sol-gel

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