CN101841022A - Method for preparing cathode material lithium manganate of lithium ion battery - Google Patents

Method for preparing cathode material lithium manganate of lithium ion battery Download PDF

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Publication number
CN101841022A
CN101841022A CN201010175808A CN201010175808A CN101841022A CN 101841022 A CN101841022 A CN 101841022A CN 201010175808 A CN201010175808 A CN 201010175808A CN 201010175808 A CN201010175808 A CN 201010175808A CN 101841022 A CN101841022 A CN 101841022A
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China
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powder
lithium manganate
lithium
lithium ion
ion battery
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CN201010175808A
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Inventor
吴显明
何则强
麻明友
陈上
肖卓炳
刘建本
陈良钢
陈善文
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XIANGXI AUTONOMOUS PREFECTURE MINERALS AND NEW MATERIAL TECHNOLOGICAL INNOVATION SERVICE CENTER
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XIANGXI AUTONOMOUS PREFECTURE MINERALS AND NEW MATERIAL TECHNOLOGICAL INNOVATION SERVICE CENTER
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Priority to CN201010175808A priority Critical patent/CN101841022A/en
Publication of CN101841022A publication Critical patent/CN101841022A/en
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Abstract

The invention discloses a method for preparing a cathode material lithium manganate of a lithium ion battery, which comprises the following steps of: adding Li(CH3COO).2H2O and Al(NO3)3.9H2O into ethylene glycol monomethyl ether, adding PO(OC4H9)3 and Ti(OC4H9)4 after the Li(CH3COO).2H2O and Al(NO3)3.9H2O are completely dissolved, and continuously stirring the mixed solution to ensure the solution is not precipitated; and adding LiaMn2-bMbO4 powder into the prepared solution, adding H3BO3 with stirring, evaporating to dryness and drying the mixed solution after the stirring, calcining the dried powder in a muffle furnace, naturally cooling the calcined powder and grinding the cooled powder to obtain lithium manganate or doped lithium manganate powder of which surfaces are coated with yLi1+xTi2-x(PO4)3.(1-y)Li3BO3. The cathode material of the lithium ion battery prepared by the method of the invention effectively prevents the lithium manganate from being dissolved, and simultaneously does not influence the intercalation and de-intercalation of lithium ions in charge and discharge processes because a coating substance is a lithium ion conductor so as to achieve relatively higher cycle performance.

Description

A kind of preparation method of lithium cell anode material lithium manganate
Technical field
The present invention relates to a kind of preparation method of lithium cell anode material lithium manganate.
Background technology
The positive electrode of commercialization lithium ion battery mostly is LiCoO at present 2Because Co scarcity of resources, its cost is far above negative pole, account for more than 1/3rd of battery total cost, make the large-scale application of lithium ion battery, especially the application in electric automobiles is restricted, thereby the cost that how to reduce anode material for lithium-ion batteries becomes the key of lithium ion battery material research.
At LiCoO 2, LiNiO 2And LiMn 2O 4In three kinds of common lithium ion battery 4V level positive electrodes, spinel lithium manganate is with low cost and environmentally friendly and become the research focus of anode material for lithium-ion batteries with it.LiMn 2O 4Shortcoming be that cycle performance is undesirable, influence LiMn 2O 4One of reason of cycle performance is LiMn in cyclic process 2O 4In Mn 3+Disproportionated reaction has taken place, the Mn of generation 2+Can be dissolved in the electrolyte, thereby cause the loss of active material and the destruction of crystal structure, cause the reduction of capacity.The present invention is at LiMn 2O 4And Li doped Mn 2O 4A kind of new coating processing is carried out on the surface, thereby suppresses the dissolving of LiMn2O4, improves LiMn 2O 4And Li doped Mn 2O 4Cycle performance.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of lithium cell anode material lithium manganate.
With Li (CH 3COO) 2H 2O and Al (NO 3) 39H 2O joins in the EGME, treats to dissolve fully the back and adds PO (OC 4H 9) 3And Ti (OC 4H 9) 4And constantly stir, guarantee that solution does not precipitate.Adopt solid phase or liquid phase reactor then, press the synthetic LiMn2O4 of known technology or doping type lithium manganate, i.e. Li aMn 2-bM bO 4(M=Cr, Ni; 0.96≤a≤1.06,0≤b≤0.1) powder.Then with Li aMn 2-bM bO 4Powder joins in the above-mentioned solution for preparing, and adds H when stirring 3BO 3, stir after 2 hours evaporate to dryness and 120 ℃ of dryings 2 hours, the powder that drying is obtained 750 ℃ of calcinings 0.5-5 hour in Muffle furnace, natural cooling, porphyrize obtain the surface and coat yLi 1+xAl xTi 2-x(PO 4) 3(1-y) Li 3BO 3LiMn2O4 or doping type lithium manganate powder (wherein 0≤x≤2,0≤y≤1).
In whole process of preparation, Li (CH 3COO) 2H 2O, Al (NO 3) 39H 2O, Ti (OC 4H 9) 4, PO (OC 4H 9) 3, H 3BO 3The ratio of amount of substance be (1-3): (0-2): (0-2): (0-3): (0-1), and LiMn 2O 4And Li doped Mn 2O 4Surface coated mass percent is controlled in 10%.
Li 1+xAl xTi 2-x(PO 4) 3Be a kind of lithium ion conductor of function admirable, its ionic conductivity reaches 7 * 10 -4S.cm -1, and Li 3BO 3Be lithium ion conductor also be good flux, these two kinds of materials mix to coat can make the LiMn2O4 surface coat better, when effectively suppressing the LiMn2O4 dissolving, because coating material is lithium ion conductor, can not influence the embedding of lithium ion in the charge and discharge process and deviate from, thereby have better cycle performance.
Embodiment:
Embodiment 1
With Li 2CO 3(99%) and electrolytic manganese dioxide (99%) mix by the ratio of 1.05: 2 amount of substance, fully grinds and be placed in the Muffle furnace 530 ℃ of heat treatments 10 hours, and then in 750 ℃ of heat treatments 24 hours, product cooled off with stove, obtains LiMn 2O 4
With 0.7 mole of Li (CH 3COO) 2H 2O joins in 1200 milliliters of EGMEs, treats to dissolve fully the PO (OC that the back adds 0.075 mole 4H 9) 3Ti (OC with 0.05 mole 4H 9) 4And constantly stir, take by weighing 925 gram LiMn then 2O 4Join in the above-mentioned solution, add 0.225 mole H simultaneously again 3BO 3, said mixture is stirred after 2 hours in 80 ℃ of evaporates to dryness, 120 ℃ of dryings are 2 hours then, the powder that drying is obtained 750 ℃ of calcinings 1 hour in Muffle furnace, natural cooling, porphyrize obtain surperficial coated lithium ion mixed conductor 0.1LiTi 2(PO 4) 30.9Li 3BO 3LiMn 2O 4Powder, surface coated mass percent are 3%, and the initial capacity of synthetic material is 114mAh/g, and 300 circulation volume conservation rates are greater than 80%.
Embodiment 2
With Li 2CO 3(99%), electrolytic manganese dioxide (99%), Cr 2O 3Ratio by 1.05: 1.9: 0.1 amount of substances mixes, and fully grinds to be placed in the Muffle furnace 530 ℃ and to handle 10 hours, and then handles 24 hours in 750 ℃, and product cools off with stove, obtains LiMn 1.9Cr 0.1O 4
With 0.5375 mole of Li (CH 3COO) 2H 2O and 0.0375 mole of Al (NO 3) 39H 2O joins in 1600 milliliters of EGMEs, treats to dissolve fully the PO (OC that the back adds 0.375 mole 4H 9) 3Ti (OC with 0.2125 mole 4H 9) 4And constantly stir, take by weighing 1948 gram LiMn 1.9Cr 0.1O 4Join in the above-mentioned solution, and then add 0.125 mole H 3BO 3, constantly stir said mixture after 2 hours in 80 ℃ of evaporates to dryness, 120 ℃ of dryings are 2 hours then, the powder that drying is obtained 650 ℃ of calcinings 6 hours in Muffle furnace, natural cooling, porphyrize obtain surperficial coated lithium ion mixed conductor 0.5Li 1.3Al 0.3Ti 1.7(PO 4) 30.5Li 3BO 3LiMn 1.9Cr 0.1O 4Powder, surface coated mass percent are 3%, and the initial capacity of synthetic material is 117mAh/g, and 300 circulation volume conservation rates are greater than 80%.
Embodiment 3
With Li 2CO 3(99%), electrolytic manganese dioxide (99%), NiO be by 1.05: 1.9: 0.1 mixed in molar ratio, fully grinds to be placed in the Muffle furnace 530 ℃ and to handle 10 hours, and then handled 24 hours in 750 ℃, product cools off with stove, obtains LiMn 1.9Ni 0.1O 4
With 0.705 mole of Li (CH 3COO) 2H 2O and 0.405 mole of Al (NO 3) 39H 2O joins in 2000 milliliters of ethanol, treats to dissolve fully the PO (OC that the back adds 0.675 mole 4H 9) 3Ti (OC with 0.045 mole 4H 9) 4And constantly stir, take by weighing 2974 gram LiMn 1.9Ni 0.1O 4Join in the above-mentioned solution, and then add 0.075 mole H 3BO 3, constantly stir said mixture after 2 hours in 80 ℃ of evaporates to dryness, 120 ℃ of dryings are 2 hours then, the powder that drying is obtained 650 ℃ of calcinings 6 hours in Muffle furnace, natural cooling, porphyrize obtain surperficial coated lithium ion mixed conductor 0.9Li 2.8Al 1.8Ti 0.2(PO 4) 30.1Li 3BO 3LiMn 1.9Ni 0.1O 4Powder, surface coated mass percent are 3%, and the initial capacity of synthetic material is 115mAh/g, and 300 circulation volume conservation rates are greater than 80%.

Claims (3)

1. the preparation method of a lithium cell anode material lithium manganate is characterized in that the (CH with Li 3COO) 2H 2O and Al (NO 3) 39H 2O joins in the EGME, treats to dissolve fully the back and adds PO (OC 4H 9) 3And Ti (OC 4H 9) 4And constantly stir, guarantee that solution does not precipitate.Adopt solid phase or liquid phase reactor then, press the synthetic LiMn2O4 of known technology or doping type lithium manganate, i.e. Li aMn 2-bM bO 4(M=Cr, Ni; 0.96≤a≤1.06,0≤b≤0.1) powder.Then with Li aMn 2-bM bO 4Powder joins in the above-mentioned solution for preparing, and adds H when stirring 3BO 3, stir after 2 hours evaporate to dryness and 120 ℃ of dryings 2 hours, the powder that drying is obtained 750 ℃ of calcinings 0.5-5 hour in Muffle furnace, natural cooling, porphyrize obtain the surface and coat yLi 1+xAl xTi 2-x(PO 4) 3(1-y) Li 3BO 3LiMn2O4 or doping type lithium manganate powder (wherein 0≤x≤2,0≤y≤1).
2. the preparation method of a kind of lithium cell anode material lithium manganate according to claim 1 is characterized in that Li (CH 3COO) 2H 2O, Al (NO 3) 39H 2O, Ti (OC 4H 9) 4, PO (OC 4H 9) 3, H 3BO 3The ratio of amount of substance be (1-3): (0-2): (0-2): (0-3): (0-1).
3. the preparation method of a kind of lithium cell anode material lithium manganate according to claim 1 is characterized in that LiMn 2O 4And Li doped Mn 2O 4Surface coated mass percent is controlled in 10%.
CN201010175808A 2010-05-13 2010-05-13 Method for preparing cathode material lithium manganate of lithium ion battery Pending CN101841022A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102332584A (en) * 2011-10-18 2012-01-25 无锡晶石新型能源有限公司 Liquid phase coating method of lithium manganate
CN103490055A (en) * 2013-09-06 2014-01-01 中国海洋石油总公司 Preparation method of nickel cobalt lithium manganate composite anode material
CN104183849A (en) * 2014-08-12 2014-12-03 江苏大学 Preparation method of solid solution positive material covering surface of fast ionic conductor
CN103456942B (en) * 2013-08-20 2016-01-20 中信大锰矿业有限责任公司大新锰矿分公司 A kind of LiMn2O4 liquid-coating method
CN107437619A (en) * 2017-07-18 2017-12-05 南京创源天地动力科技有限公司 A kind of anode for lithium battery material and preparation method thereof
CN109004212A (en) * 2018-06-22 2018-12-14 中南大学 A kind of big multiplying power manganate cathode material for lithium and preparation method thereof
CN111943272A (en) * 2020-07-13 2020-11-17 广东邦普循环科技有限公司 Method for eliminating residual lithium by lithium transition metal oxide and application thereof
US10930980B2 (en) 2015-12-23 2021-02-23 Industrial Technology Research Institute Additive formulation and composition for lithium ion battery and lithium ion battery comprising the same
CN112635748A (en) * 2019-10-09 2021-04-09 北京卫蓝新能源科技有限公司 Composite positive electrode material of lithium ion battery and preparation method thereof

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CN101038965A (en) * 2006-03-14 2007-09-19 深圳市比克电池有限公司 Method for preparing modified spinelle manganic acid lithium material and lithium secondary battery

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CN101038965A (en) * 2006-03-14 2007-09-19 深圳市比克电池有限公司 Method for preparing modified spinelle manganic acid lithium material and lithium secondary battery

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102332584A (en) * 2011-10-18 2012-01-25 无锡晶石新型能源有限公司 Liquid phase coating method of lithium manganate
CN102332584B (en) * 2011-10-18 2013-09-18 无锡晶石新型能源有限公司 Liquid phase coating method of lithium manganate
CN103456942B (en) * 2013-08-20 2016-01-20 中信大锰矿业有限责任公司大新锰矿分公司 A kind of LiMn2O4 liquid-coating method
CN103490055A (en) * 2013-09-06 2014-01-01 中国海洋石油总公司 Preparation method of nickel cobalt lithium manganate composite anode material
CN104183849A (en) * 2014-08-12 2014-12-03 江苏大学 Preparation method of solid solution positive material covering surface of fast ionic conductor
US10930980B2 (en) 2015-12-23 2021-02-23 Industrial Technology Research Institute Additive formulation and composition for lithium ion battery and lithium ion battery comprising the same
CN107437619A (en) * 2017-07-18 2017-12-05 南京创源天地动力科技有限公司 A kind of anode for lithium battery material and preparation method thereof
CN109004212A (en) * 2018-06-22 2018-12-14 中南大学 A kind of big multiplying power manganate cathode material for lithium and preparation method thereof
CN112635748A (en) * 2019-10-09 2021-04-09 北京卫蓝新能源科技有限公司 Composite positive electrode material of lithium ion battery and preparation method thereof
CN112635748B (en) * 2019-10-09 2022-11-15 北京卫蓝新能源科技有限公司 Composite positive electrode material of lithium ion battery and preparation method thereof
CN111943272A (en) * 2020-07-13 2020-11-17 广东邦普循环科技有限公司 Method for eliminating residual lithium by lithium transition metal oxide and application thereof
CN111943272B (en) * 2020-07-13 2022-11-15 广东邦普循环科技有限公司 Method for eliminating residual lithium by lithium transition metal oxide and application thereof

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Application publication date: 20100922