CN108336327A - A method of doping AL ion coated lithium tetraborates prepare LiMn2O4 - Google Patents

A method of doping AL ion coated lithium tetraborates prepare LiMn2O4 Download PDF

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Publication number
CN108336327A
CN108336327A CN201711492653.6A CN201711492653A CN108336327A CN 108336327 A CN108336327 A CN 108336327A CN 201711492653 A CN201711492653 A CN 201711492653A CN 108336327 A CN108336327 A CN 108336327A
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Prior art keywords
lithium
limn2o4
solution
doping
tetraborates
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Chinese (zh)
Inventor
万辉
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JIANGSU KING LITHIUM CELL CO Ltd
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JIANGSU KING LITHIUM CELL CO Ltd
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Priority to CN201711492653.6A priority Critical patent/CN108336327A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 present invention adulterates the method that AL ion coated lithium tetraborates prepare LiMn2O4, by AL3+It is doped to inside LiMn2O4 and coats Li on surface2O‑2B2O3, carrying out double sintering and reasonably controlling the condition of sintering obtaining mixing AL after obtained lithium manganate material and aluminium oxide being mixed in preparation process3+Lithium manganate material, while by it in lithium tetraborate（Li2O‑2B2O3）Solution in carry out dispersion stirring, it is then dry, broken, screening obtain Li2O‑2B2O3The LiMn2O4 of cladding improves LiMn2O4 performance by the method being mixed with, and high temperature cyclic performance, specific capacity all have significant improvement, and capacity attenuation also reduces.

Description

A method of doping AL ion coated lithium tetraborates prepare LiMn2O4
Technical field
The present invention relates to a kind of methods that doping AL ion coated lithium tetraborates prepare LiMn2O4.
Background technology 1
Recently as using battery as the electric hybrid automobile of power and the emergence of pure electric automobile, the demand of battery is increasing Add, while the performance requirement of battery is also being improved, LiMn2O4（LiMn2O4）As optimal power battery material, it has The features such as energy density height, discharging voltage balance, use temperature range be wide, cheap, synthesis is resourceful and opened extensively Hair uses；But the features such as its high temperature cyclic performance is poor, specific capacity is low, capacity attenuation is fast, also affects its development simultaneously.
Invention content
The technical problem to be solved by the invention is to provide a kind of high temperature cyclic performance that can improve LiMn2O4, specific volumes Measure and reduce the method that the doping AL ion coated lithium tetraborates of itself capacity fade performance prepare LiMn2O4.
A kind of method that doping AL ion coated lithium tetraborates prepare LiMn2O4 of the present invention, it is characterised in that：Including with Lower step,
（1）By MnO2、Li2CO3The molar ratio of mixing, lithium content and manganese content is 0.45-0.55；
（2）By step（1）In mixture after mixing, be sintered 9- at a temperature of 400-600 DEG C in air Muffle furnace 15h, cooling, broken, sieving obtain LiMn2O4（LiMn2O4）；
（3）By step（2）In obtained lithium manganate material and aluminium oxide according to stoichiometric ratio AL3+/ M=0.002-0.005 is equal Even mixing, wherein M are the total contents of LiMn2O4；
（4）15-30h double sinterings are carried out at a temperature of by the material mixed 700-900 DEG C in air Muffle furnace, then with stove Warm natural cooling is crushed, and sieving obtains mixing AL3+Lithium manganate material；
（5）Again by step（4）In mix AL3+Lithium manganate material be added to the lithium tetraborate of 0.3-0.6mol/L（Li2O- 2B2O3）Dispersion stirring is carried out in solution, which persistently stirs 2-4h in 60-80 DEG C of water-bath, then filters, dry；
（6）By step（5）Material after middle drying roasts furnace cooling after 3-5h at 300-450 DEG C, is crushed after taking-up, mistake Sieve, obtains Li2O-2B2O3Cladding mixes AL3+Lithium manganate material；
Preferably,
The step（1）The molar ratio of middle lithium and manganese is 0.52；
The step（2）Middle sintering temperature is 500 DEG C, soaking time 10h；
The step（3）Middle AL3+/M=0.003；
The step（5）Middle solution is the lithium tetraborate of 0.4mol/L（Li2O-2B2O3）Solution；
Preferably,
The step（1）The molar ratio of middle lithium and manganese is 0.45；
The step（2）Middle sintering temperature is 400 DEG C, soaking time 10h；
The step（3）Middle AL3+/M=0.003；
The step（5）Middle solution is the lithium tetraborate of 0.4mol/L（Li2O-2B2O3）Solution；
Preferably,
The step（1）The molar ratio of middle lithium and manganese is 0.50；
The step（2）Middle sintering temperature is 500 DEG C, soaking time 10h；
The step（3）Middle AL3+/M=0.003；
The step（5）Middle solution is the lithium tetraborate of 0.4mol/L（Li2O-2B2O3）Solution.
The present invention adulterates the method that AL ion coated lithium tetraborates prepare LiMn2O4, by AL3+It is doped to inside LiMn2O4 simultaneously And coat Li on surface2O-2B2O3, in preparation process will obtained lithium manganate material and aluminium oxide mix after carry out double sintering And the condition for reasonably controlling sintering obtains mixing AL3+Lithium manganate material, while by it in lithium tetraborate（Li2O-2B2O3）'s Dispersion stirring is carried out in solution, then dry, broken, screening obtains Li2O-2B2O3The LiMn2O4 of cladding, passes through what is be mixed with Method improves LiMn2O4 performance, and high temperature cyclic performance, specific capacity all have significant improvement, and capacity attenuation also drops It is low.
Specific implementation mode
Technical problem to be solved by the invention is to provide a kind of high temperature cyclic performance that can improve LiMn2O4, specific capacities With the AL for reducing itself capacity fade performance3+Adulterate lithium tetraborate（Li2O-2B2O33）Coat the preparation method of LiMn2O4.
A method of doping AL ion coated lithium tetraborates prepare LiMn2O4, include the following steps,
（1）By MnO2、Li2CO3The molar ratio of mixing, lithium content and manganese content is 0.45-0.55；
（2）By step（1）In mixture after mixing, be sintered 9- at a temperature of 400-600 DEG C in air Muffle furnace 15h, cooling, broken, sieving obtain LiMn2O4（LiMn2O4）；
（3）By step（2）In obtained lithium manganate material and aluminium oxide according to stoichiometric ratio AL3+/ M=0.002-0.005 is equal Even mixing, wherein M are the total contents of LiMn2O4；
（4）15-30h double sinterings are carried out at a temperature of by the material mixed 700-900 DEG C in air Muffle furnace, then with stove Warm natural cooling is crushed, and sieving obtains mixing AL3+Lithium manganate material；
（5）Again by step（4）In mix AL3+Lithium manganate material be added to the lithium tetraborate of 0.3-0.6mol/L（Li2O- 2B2O3）Dispersion stirring is carried out in solution, which persistently stirs 2-4h in 60-80 DEG C of water-bath, then filters, dry；
（6）By step（5）Material after middle drying roasts furnace cooling after 3-5h at 300-450 DEG C, is crushed after taking-up, mistake Sieve, obtains Li2O-2B2O3Cladding mixes AL3+Lithium manganate material；
Preferably,
The step（1）The molar ratio of middle lithium and manganese is 0.52；
The step（2）Middle sintering temperature is 500 DEG C, soaking time 10h；
The step（3）Middle AL3+/M=0.003；
The step（5）Middle solution is the lithium tetraborate of 0.4mol/L（Li2O-2B2O3）Solution.
Embodiment one：
The AL of the present invention3+Adulterate Li2O-2B2O3The preparation method for coating lithium manganate material, includes the following steps：
（1）By MnO2、Li2CO3The molar ratio of mixing, lithium and manganese is 0.45；
（2）By step（1）In mixture after mixing, 9h, cooling broken sieving are sintered at 400 DEG C in air Muffle furnace After obtain LiMn2O4 LiMn2O4；
（3）By step（2）In obtained lithium manganate material and aluminium oxide in three-dimensional material mixer according to stoichiometric ratio AL3+/M= 0.003（Wherein, M LiMn2O4s）Uniformly mixing,
（4）The material mixed is subjected to double sintering in air Muffle furnace, sintering process is the heating from room temperature to 600 DEG C 5 DEG C/min of rate, from 600 DEG C to 700 DEG C, 2 DEG C/min of heating rate keeps the temperature 11 h under 700 DEG C of temperature environments, then with Furnace temperature natural cooling is crushed, and sieving obtains mixing AL3+Manganate cathode material for lithium；
（5）Again by step（4）In mix AL3+Lithium manganate material be added to the lithium tetraborate of 0.4mol/L（Li2O-2B2O3）It is molten Dispersion stirring is carried out in liquid, which persistently stirs 2h in 60 DEG C of water-baths, then filters, dry；
（6）By step（5）Material after middle drying roasts furnace cooling after 3h at 300 DEG C, is crushed after taking-up, and sieving obtains four Lithium borate（Li2O-2B2O3）Cladding mixes AL3+Lithium manganate material.
Embodiment two：
The AL of the present invention3+Adulterate Li2O-2B2O3The preparation method for coating lithium manganate material, includes the following steps：
（1）By MnO2、Li2CO3The molar ratio of mixing, lithium and manganese is 0.50；
（2）By step（1）In mixture after mixing, in air Muffle furnace at 500 DEG C be sintered 10h, cooling be crushed LiMn2O4 LiMn is obtained after sieve2O4；
（3）By step（2）In obtained lithium manganate material and aluminium oxide in three-dimensional material mixer according to stoichiometric ratio AL3+/M= 0.003（Wherein, M LiMn2O4s）Uniformly mixing,
（4）The material mixed is subjected to double sintering in air Muffle furnace, sintering process is the heating from room temperature to 600 DEG C 5 DEG C/min of rate, from 600 DEG C to 780 DEG C, 2 DEG C/min of heating rate keeps the temperature 11 h under 780 DEG C of temperature environments, then with Furnace temperature natural cooling is crushed, and sieving obtains mixing AL3+Manganate cathode material for lithium；
（5）Again by step（4）In mix AL3+ lithium manganate material be added to the lithium tetraborate of 0.4mol/L（Li2O-2B2O3）It is molten Dispersion stirring is carried out in liquid, which persistently stirs 2h in 60 DEG C of water-baths, then filters, dry；
（6）By step（5）Material after middle drying roasts furnace cooling after 4h at 400 DEG C, is crushed after taking-up, and sieving obtains four Lithium borate（Li2O-2B2O3）Cladding mixes AL3+Manganate cathode material for lithium.

Claims (4)

1. a kind of method that doping AL ion coated lithium tetraborates prepare LiMn2O4, it is characterised in that：Include the following steps,
（1）By MnO2、Li2CO3The molar ratio of mixing, lithium content and manganese content is 0.45-0.55；
（2）By step（1）In mixture after mixing, be sintered 9- at a temperature of 400-600 DEG C in air Muffle furnace 15h, cooling, broken, sieving obtain LiMn2O4（LiMn2O4）；
（3）By step（2）In obtained lithium manganate material and aluminium oxide according to stoichiometric ratio AL3+/ M=0.002-0.005 is uniform Mixing, wherein M is the total content of LiMn2O4；
（4）15-30h double sinterings are carried out at a temperature of by the material mixed 700-900 DEG C in air Muffle furnace, then with stove Warm natural cooling is crushed, and sieving obtains mixing AL3+Lithium manganate material；
（5）Again by step（4）In mix AL3+Lithium manganate material be added to the lithium tetraborate of 0.3-0.6mol/L（Li2O- 2B2O3）Dispersion stirring is carried out in solution, which persistently stirs 2-4h in 60-80 DEG C of water-bath, then filters, dry；
（6）By step（5）Material after middle drying roasts furnace cooling after 3-5h at 300-450 DEG C, is crushed after taking-up, mistake Sieve, obtains Li2O-2B2O3Cladding mixes AL3+Lithium manganate material.
2. the method that doping AL ion coated lithium tetraborates prepare LiMn2O4 according to claim 1, it is characterised in that：
The step（1）The molar ratio of middle lithium and manganese is 0.52；
The step（2）Middle sintering temperature is 500 DEG C, soaking time 10h；
The step（3）Middle AL3+/M=0.003；
The step（5）Middle solution is the lithium tetraborate of 0.4mol/L（Li2O-2B2O3）Solution.
3. the method that doping AL ion coated lithium tetraborates prepare LiMn2O4 according to claim 1, it is characterised in that：
The step（1）The molar ratio of middle lithium and manganese is 0.45；
The step（2）Middle sintering temperature is 400 DEG C, soaking time 10h；
The step（3）Middle AL3+/M=0.003；
The step（5）Middle solution is the lithium tetraborate of 0.4mol/L（Li2O-2B2O3）Solution.
4. the method that doping AL ion coated lithium tetraborates prepare LiMn2O4 according to claim 1, it is characterised in that：
The step（1）The molar ratio of middle lithium and manganese is 0.50；
The step（2）Middle sintering temperature is 500 DEG C, soaking time 10h；
The step（3）Middle AL3+/M=0.003；
The step（5）Middle solution is the lithium tetraborate of 0.4mol/L（Li2O-2B2O3）Solution.
CN201711492653.6A 2017-12-30 2017-12-30 A method of doping AL ion coated lithium tetraborates prepare LiMn2O4 Pending CN108336327A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110627127A (en) * 2019-08-30 2019-12-31 湖南金富力新能源股份有限公司 Lithium manganate positive electrode material and preparation method and application thereof
CN116425204A (en) * 2023-04-28 2023-07-14 巴斯夫杉杉电池材料有限公司 Spinel type lithium manganate, preparation method thereof and lithium ion battery
WO2023179447A1 (en) * 2022-03-23 2023-09-28 湖南长远锂科新能源有限公司 Al/b co-coated positive electrode material, and preparation method therefor

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CN105355911A (en) * 2015-11-28 2016-02-24 中信大锰矿业有限责任公司大新锰矿分公司 Preparation method of aluminum oxide coated lithium nickel manganese cobalt cathode material
CN105655576A (en) * 2016-04-12 2016-06-08 北京晶晶星科技有限公司 Coated modified lithium manganate and preparation method thereof

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Publication number Priority date Publication date Assignee Title
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
CN103500827A (en) * 2013-10-11 2014-01-08 宁德新能源科技有限公司 Lithium ion battery and multi-element positive material thereof as well as preparation method of multi-element positive material
CN103606670A (en) * 2013-12-03 2014-02-26 苏州科大微龙信息技术有限公司 Lithium manganate positive electrode material of power lithium ion battery and preparation method thereof
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110627127A (en) * 2019-08-30 2019-12-31 湖南金富力新能源股份有限公司 Lithium manganate positive electrode material and preparation method and application thereof
WO2023179447A1 (en) * 2022-03-23 2023-09-28 湖南长远锂科新能源有限公司 Al/b co-coated positive electrode material, and preparation method therefor
CN116425204A (en) * 2023-04-28 2023-07-14 巴斯夫杉杉电池材料有限公司 Spinel type lithium manganate, preparation method thereof and lithium ion battery
CN116425204B (en) * 2023-04-28 2024-03-22 巴斯夫杉杉电池材料有限公司 Spinel type lithium manganate, preparation method thereof and lithium ion battery

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Application publication date: 20180727