CN106784788A - One kind prepares porous LiMn by template of carbon ball2O4Method - Google Patents

One kind prepares porous LiMn by template of carbon ball2O4Method Download PDF

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Publication number
CN106784788A
CN106784788A CN201611202862.8A CN201611202862A CN106784788A CN 106784788 A CN106784788 A CN 106784788A CN 201611202862 A CN201611202862 A CN 201611202862A CN 106784788 A CN106784788 A CN 106784788A
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China
Prior art keywords
limn
carbon ball
solution
aqueous solution
porous
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CN201611202862.8A
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Chinese (zh)
Inventor
孙雅馨
钱兵
岳军伟
宋修梅
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Anhui University of Technology AHUT
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Anhui University of Technology AHUT
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Priority to CN201611202862.8A priority Critical patent/CN106784788A/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
    • H01M4/48—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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 one kind porous LiMn is prepared by template of carbon ball2O4Method, belong to porous material preparing technical field.The method specific steps include：A, using lithium nitrate and manganese nitrate or using lithium acetate and manganese acetate as raw material, be stoichiometrically configured to the aqueous solution；B, to adding a certain amount of citric acid in the above-mentioned aqueous solution, and adjust the pH value of the aqueous solution to 7~9, add a certain amount of carbon ball, be sufficiently stirred for；C, the suspension for stirring above-mentioned preparation in a heated condition, until forming gel, are then dried, and obtain predecessor；D, by predecessor elder generation pre-burning calcine again, you can obtain the LiMn of loose structure2O4Monophase materialses.A kind of easy to operate the invention provides process is simple, with low cost porous LiMn2O4Preparation method.

Description

One kind prepares porous LiMn by template of carbon ball2O4Method
Technical field
The invention belongs to porous material preparing technical field, and in particular to a kind of porous LiMn2O4Preparation method.
Background technology
The LiMn of spinel structure2O4Environmentally friendly with abundant raw material, operating voltage is higher, overcharging resisting and security Good the advantages of, be most potential replacement LiCoO2One of Li ion battery positive electrodes.In order to meet answering for high power system With requiring, it is necessary to positive electrode of the development with rapid kinetics.Nanoporous LiMn2O4The development of positive electrode is in recent years The hot issue of research.Nanometer perforated electrodes can shorten the diffusion length of Li ions, be especially advantageous for electrolyte permeability to electrode In material, increase effective contact area, and then the transmission beneficial to electric charge between electrode and electrolyte.What is be especially interconnected is more Pore structure can preferably Li ions deintercalation causes repeatedly volumetric expansion and contraction during buffer cycles.Therefore, prepare many The LiMn in hole2O4Positive electrode has great practical value.
At present, porous LiMn2O4Preparation method be mainly carbonate obtained as predecessor using coprecipitation, then pass through Crossing calcining can obtain the um porous material of self-assembly.The preparation method is more complicated, especially by coprecipitated The sediment that shallow lake method is obtained will carry out repeated multiple times washing, the Mn (CO for obtaining3)2Sediment is obtained after first once being calcined MnO2, then MnO2Solution is reconfigured to LiOH to be sufficiently stirred for and mix, after being evaporated, then carries out reaction-sintered, be made porous material Material.
Therefore, a kind of process is simple is sought, easy to operate, with low cost porous LiMn2O4Preparation method have it is important Practical significance.
The content of the invention
In order to overcome the deficiencies in the prior art, the technical problem to be solved in the present invention be to provide it is a kind of easy and effective, with carbon Ball prepares porous LiMn for template2O4Method.
In order to solve the above technical problems, the present invention is achieved by the following technical programs, comprise the following steps：
(1) using lithium nitrate and manganese nitrate or using lithium acetate and manganese acetate as raw material, Li in molar ratio:Mn=1:2 Ratio matched, and be made the aqueous solution.
(2) to step (1) prepare the aqueous solution in add a certain amount of complexing agent citric acid；Wherein：Citric acid and step (1) mol ratio of the cation in solution is 1：2.
(3) pH value of set-up procedure (2) aqueous solution, is slowly added to appropriate NH3·H2The pH value of solution is adjusted to 7~9 by O, Form colloidal sol.
(4) add carbon ball in the colloidal sol for preparing to step (3), and be sufficiently stirred for so that carbon ball is uniformly dispersed, obtaining suspended Liquid；Wherein：Carbon ball is 1~20 with the mol ratio of Mn ions in solution:1.
(5) suspension prepared in whipping step (4) under the conditions of 80 DEG C, until forming gel.
(6) gel that step (5) is obtained is dried into 1h under the conditions of 160 DEG C, is ground after room temperature is dropped to and obtain predecessor.
(7) 4~10h of pre-burning after the predecessor that step (6) is obtained being heated into 400~550 DEG C, is cooled to room temperature afterwards, It is fully ground, is obtained powder sample.
(8) powder sample of step (7) is calcined into 4~24h at 600~850 DEG C, obtains the LiMn of loose structure2O4Single-phase material Material.
Optimize as one kind, in the step (7), calcined temperature is 500 DEG C, and burn-in time is 6h.
Optimize as one kind, in the step (8), calcining heat is 650 DEG C, and calcination time is 6h.
Compared with prior art, the present invention has following technique effect：
(1) process is simple that the present invention is used, preparation condition is gentle, and calcining heat is low, and heat treatment time is short, saves energy Source.
(2) using carbon ball as template, less than LiMn2O4Can be easy to by being oxidized to gas at a temperature of phase Ground is removed, and leaves hole or duct.
(3) the porous LiMn obtained using the method2O4The specific surface area of material is higher, is 10.43~14.69m2/g。
Brief description of the drawings
Fig. 1 is porous LiMn obtained in the embodiment of the present invention 12O4X-ray diffraction (XRD) collection of illustrative plates.
Fig. 2 is porous LiMn obtained in the embodiment of the present invention 12O4SEM (SEM) photo.
Fig. 3 is porous LiMn obtained in the embodiment of the present invention 12O4N2Adsorption and desorption curve.
Specific embodiment
In order to further appreciate that technology contents of the invention, below in conjunction with drawings and Examples in detail the present invention, but this hair are described in detail It is bright to be not limited to following embodiments.
Embodiment 1
Weigh the LiNO of 0.69g3, the Mn (NO of 4.65ml3)2(solution of mass fraction 50%, similarly hereinafter), 3.15g's C6H8O7·H2O, is dissolved into deionized water, is sufficiently stirred for, and adds appropriate NH3·H2The pH value of solution is adjusted to 8 by O.Again To the carbon ball that 1.2g is added in solution.Magnetic stirring apparatus temperature is set as 80 DEG C, above-mentioned solution is placed on magnetic stirring apparatus It is sufficiently stirred for, until forming gel；Gel is put into drying box, 1h is dried under conditions of 160 DEG C, through carefully grinding Afterwards, in 500 DEG C of pre-burning 6h, then it is fully ground, then sinters 6h at 650 DEG C, obtains porous LiMn2O4。
Wherein carbon ball is prepared using hydro-thermal method.Specific method is：With C6H12O6·H2O is raw material, will 1.6gC6H12O6·H2O is dissolved into the deionized water of 40ml, is made into the solution that concentration is 0.5M, in placing into 50ml reactors, In hydro-thermal reaction 6h at 180 DEG C.After reaction terminates, hydrothermal product is carried out into multiple washing and alcohol is washed, after drying 5h through 80 DEG C, Can obtain the more uniform about carbon ball of 500nm of size.
Fig. 1 is the porous LiMn prepared by the present embodiment2O4XRD spectrum, the collection of illustrative plates shows that product is LiMn2O4It is single Phase.
Fig. 2 is porous LiMn prepared by the present embodiment2O4SEM spectrum, collection of illustrative plates shows, has prepared porous LiMn2O4 Material.Pore-size distribution is in the range of 0.1~1um.
Fig. 3 is porous LiMn obtained in the present embodiment2O4N2Adsorption and desorption curve.Specific surface area is tested and shown, this reality Apply the porous LiMn of example preparation2O4Specific surface area is 11.50m2/g。
Embodiment 2
Weigh the LiNO of 0.69g3, 4.65gmlMn (NO3)2, the C of 3.15g6H8O7·H2O, is dissolved into deionized water, fills Divide stirring, add appropriate NH3·H2The pH value of solution is adjusted to 8 by O.Again to the carbon ball that 0.24g is added in solution.Carbon ball Preparation method and process are with embodiment 1.Above-mentioned solution is placed on magnetic stirring apparatus, is sufficiently stirred under the conditions of 80 DEG C, Until forming gel；Gel is put into drying box, 1h is dried under conditions of 160 DEG C, it is pre- in 400 DEG C after carefully grinding 8h is burnt, then is fully ground, then sinter 12h at 750 DEG C, obtain porous LiMn2O4。
Embodiment 3
Weigh the LiNO of 0.69g3, the Mn (NO of 4.65ml3)2, the C of 3.15g6H8O7·H2O, is dissolved into deionized water, It is sufficiently stirred for, adds appropriate NH3·H2The pH value of solution is adjusted to 8 by O.Again to the carbon ball that 2.4g is added in solution.Carbon ball Preparation method and process are with embodiment 1.Above-mentioned solution is placed on magnetic stirring apparatus, is sufficiently stirred under the conditions of 80 DEG C, Until forming gel；Gel is put into drying box, 1h is dried under conditions of 160 DEG C, it is pre- in 500 DEG C after carefully grinding 10h is burnt, then is fully ground, then sinter 6h at 850 DEG C, obtain porous LiMn2O4。
Embodiment 4
Weigh the CH of 1.071g3COOLi·2H2Mn (the CH of O, 4.9g3COO)2·4H2The C of O, 3.203g6H8O7·H2O is molten Solution is sufficiently stirred in deionized water, adds appropriate NH3·H2The pH value of solution is adjusted to 8 by O.Added in solution again The carbon ball of 0.12g.The preparation method and process of carbon ball are with embodiment 1.Above-mentioned solution is placed on magnetic stirring apparatus, in 80 DEG C of bars It is sufficiently stirred under part, until forming gel；Gel is put into drying box, 1h is dried under conditions of 160 DEG C, through careful After grinding, in 550 DEG C of pre-burning 5h, then it is fully ground, then sinters 10h at 650 DEG C, obtains porous LiMn2O4。
Embodiment 5
Weigh the CH of 1.071g3COOLi·2H2Mn (the CH of O, 4.9g3COO)2·4H2The C of O, 3.203g6H8O7·H2O is molten Solution is sufficiently stirred in deionized water, adds appropriate NH3·H2The pH value of solution is adjusted to 8 by O.Added in solution again The carbon ball of 1.2g.The preparation method and process of carbon ball are with embodiment 1.Above-mentioned solution is placed on magnetic stirring apparatus, in 80 DEG C of bars It is sufficiently stirred under part, until forming gel；Gel is put into drying box, 1h is dried under conditions of 160 DEG C, through careful After grinding, in 400 DEG C of pre-burning 8h, then it is fully ground, then sinters 6h at 700 DEG C, obtains porous LiMn2O4。

Claims (3)

1. one kind prepares porous LiMn by template of carbon ball2O4Method, it is characterised in that the method is comprised the following steps：
(1) using lithium nitrate and manganese nitrate or using lithium acetate and manganese acetate as raw material, Li in molar ratio:Mn=1:2 ratio Example is matched, and is made the aqueous solution；
(2) to step (1) prepare the aqueous solution in add a certain amount of complexing agent citric acid；Wherein：In citric acid and step (1) The mol ratio of the cation in solution is 1：2；
(3) pH value of set-up procedure (2) aqueous solution, is slowly added to appropriate NH3·H2The pH value of solution is adjusted to 7~9 by O, is formed Colloidal sol；
(4) add carbon ball in the colloidal sol for preparing to step (3), and be sufficiently stirred for so that carbon ball is uniformly dispersed, obtaining suspension；Its In：Carbon ball is 1~20 with the mol ratio of Mn ions in solution:1；
(5) suspension prepared in whipping step (4) under the conditions of 80 DEG C, until forming gel；
(6) gel that step (5) is obtained is dried into 1h under the conditions of 160 DEG C, is ground after room temperature is dropped to and obtain predecessor；
(7) 4~10h of pre-burning after the predecessor that step (6) is obtained being heated into 400~550 DEG C, is cooled to room temperature afterwards, carries out It is fully ground, obtains powder sample；
(8) powder sample of step (7) is calcined into 4~24h at 600~850 DEG C, obtains the LiMn of loose structure2O4Monophase materialses.
2. porous LiMn is prepared by template of carbon ball as claimed in claim 12O4Method, it is characterised in that the step (7) in, calcined temperature is 500 DEG C, and burn-in time is 6h.
3. porous LiMn is prepared by template of carbon ball as claimed in claim 12O4Method, it is characterised in that the step (8) in, calcining heat is 650 DEG C, and calcination time is 6h.
CN201611202862.8A 2016-12-23 2016-12-23 One kind prepares porous LiMn by template of carbon ball2O4Method Pending CN106784788A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1466234A (en) * 2002-06-07 2004-01-07 兴能高科技股份有限公司 Method for making positive electrode material LiMn2O4 powder of secondary cell
CN1744353A (en) * 2004-08-31 2006-03-08 中国科学院青海盐湖研究所 The preparation method of spherical spinel Li-Mn-Oxide anode material for lithium-ion batteries
CN102386389A (en) * 2010-08-31 2012-03-21 机械科学研究总院先进制造技术研究中心 High capacity cathode material of lithium ion battery and preparation method thereof
CN104681799A (en) * 2014-02-21 2015-06-03 台塑生医科技股份有限公司 Method for manufacturing lithium iron manganese phosphate/carbon cathode material and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1466234A (en) * 2002-06-07 2004-01-07 兴能高科技股份有限公司 Method for making positive electrode material LiMn2O4 powder of secondary cell
CN1744353A (en) * 2004-08-31 2006-03-08 中国科学院青海盐湖研究所 The preparation method of spherical spinel Li-Mn-Oxide anode material for lithium-ion batteries
CN102386389A (en) * 2010-08-31 2012-03-21 机械科学研究总院先进制造技术研究中心 High capacity cathode material of lithium ion battery and preparation method thereof
CN104681799A (en) * 2014-02-21 2015-06-03 台塑生医科技股份有限公司 Method for manufacturing lithium iron manganese phosphate/carbon cathode material and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YUANYUAN HU等: "("Preparation and characterization of macroporous LiNi1/3Co1/3Mn1/3O2 using carbon sphere as template"", 《MATERIALS CHEMISTRY AND PHYSICS》 *

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Application publication date: 20170531