CN104538589B - A kind of preparation method of layered lithium manganate material - Google Patents

A kind of preparation method of layered lithium manganate material Download PDF

Info

Publication number
CN104538589B
CN104538589B CN201410800741.8A CN201410800741A CN104538589B CN 104538589 B CN104538589 B CN 104538589B CN 201410800741 A CN201410800741 A CN 201410800741A CN 104538589 B CN104538589 B CN 104538589B
Authority
CN
China
Prior art keywords
preparation
lithium
glycerine
raw material
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201410800741.8A
Other languages
Chinese (zh)
Other versions
CN104538589A (en
Inventor
郭俊明
彭金辉
白红丽
苏长伟
冯莉莉
王红斌
袁明龙
汪正良
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yunnan Minzu University
Original Assignee
Yunnan Minzu University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yunnan Minzu University filed Critical Yunnan Minzu University
Priority to CN201410800741.8A priority Critical patent/CN104538589B/en
Publication of CN104538589A publication Critical patent/CN104538589A/en
Application granted granted Critical
Publication of CN104538589B publication Critical patent/CN104538589B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to a kind of preparation method of positive electrode laminated cell lithium manganate of lithium ion, be specifically reactant lithium carbonate and manganese carbonate ball milling mixing it is uniform after, add fuel glycerine, then insulation of being burnt in Muffle furnace, you can acquisition stratiform LiMnO2Electrode material.Stratiform LiMnO proposed by the invention2The preparation method of anode material for lithium-ion batteries, is not required to protective atmosphere, can be prepared in open air atmosphere, has the characteristics of simple to operate, aggregate velocity is fast.

Description

A kind of preparation method of layered lithium manganate material
Technical field
The present invention relates to the preparing technical field of anode material for lithium-ion batteries, specifically stratiform LiMnO2Preparation side Method.
Background technology
Lithium battery anode material lithium Mn oxide has low cost of material, pollution-free, high voltage, high-energy-density etc. Advantage, it is to be considered as one of most promising positive electrode by people, particularly with electrokinetic cell, LiMn2O4 has tempting Prospect, it is the study hotspot of lithium ion battery.LiMn2O4 mainly includes spinel-type LiMn2O4With layer structure LiMnO2, wherein Lithium manganate having spinel structure Stability Analysis of Structures, it is easy to accomplish industrialized production.Spinel-type LiMn2O4Theoretical specific capacity is 148mAh/g, Actual specific capacity is 120mAh/g or so, voltage platform 3.9V.Stratiform LiMnO2Theoretical capacity 285mAh/g, almost it is point Spar type LiMn2O42 times, but its synthesis is relatively difficult and unstable.
Stratiform LiMnO is prepared at present2Main method have ion-exchange process（Li+With NaMnO2Middle Na+Exchange and formed LiMnO2）, hydrothermal synthesis method, high temperature solid-state method and sol-gel process etc., but stratiform LiMnO2It must be prepared in argon gas atmosphere.
Stratiform LiMnO proposed by the invention2The preparation method of material, is not required to protective atmosphere, in open air atmosphere It can prepare, there is the characteristics of simple to operate, aggregate velocity is fast.
The content of the invention
The present invention is intended to provide one kind prepares stratiform LiMnO in air atmosphere2The method of anode material for lithium-ion batteries.
Technical scheme is as follows：The present invention uses lithium carbonate and manganese carbonate as raw material, first by lithium carbonate and carbonic acid Manganese is well mixed, and is then added glycerin solution mixing and is tuned into starchiness, Muffle furnace is heated in advance the temperature set, then Being put into equipped with the crucible for being tuned into starchiness reactant feed in Muffle furnace, combustion reaction insulation 1h, finally take out and product is housed Crucible be cooled to room temperature in atmosphere, that is, obtain stratiform LiMnO2Material.Specific synthesis step is as follows：
（1）Lithium carbonate and manganese carbonate reactant are weighed in proportion, are added appropriate absolute alcohol and are mixed lithium manganese carbonate ball milling Close uniformly, reactant mixture raw material is dried to obtain at 60 DEG C；
（2）Add appropriate glycerin solution to be well mixed with the reactant mixture raw material, it is permanent to be then placed in preheating Combustion reaction is heated in the Muffle furnace of temperature and is incubated, cooling obtains stratiform LiMnO2Material.
According to the method for claim 1, it is characterised in that the amount of the material of lithium and manganese is than row in reactant compound For Li:Mn=1 ~ 1.30:1.00, the amount ratio of the material of the lithium and manganese is preferably 1.10: 1.00.
According to the method for claim 1, it is characterised in that the addition quality of glycerine is that reactant mixture raw material is total 5 ~ 30 % of quality, the addition quality of the glycerine is preferably 10 %.
According to the method for claim 1, it is characterised in that Muffle furnace is first preheating to 500 ~ 800 DEG C, it is described pre- The temperature of hot constant temperature is preferably 700 DEG C.
According to the method for claim 1, it is characterised in that the heating combustion is carried out under conditions of Muffle furnace is closed Burn reaction.
According to the method for claim 1, it is characterised in that the heating combustion reaction is simultaneously incubated 0.5 ~ 3 h, described Time is preferably 1 ~ 2 h.
According to the method for claim 1, it is characterised in that it is described be cooled to stove is cold or air cooling after obtain stratiform LiMnO2Material, the cooling are preferably air cooling mode.
Brief description of the drawings：
Fig. 1 is Li:Mn is 1.10:1.00 under the conditions of 700 DEG C of combustion reactions are incubated 1h air coolings synthetic product XRD Figure.A. 5% glycerine, the glycerine of b. 10%, the glycerine of c. 20%, the glycerine of d. 30%, the glycerine of e. 40%；
Fig. 2 is Li:Mn is 1.05:1.00 under the conditions of 700 DEG C of combustion reactions are incubated 1h air coolings synthetic product XRD Figure.A. 5% glycerine, the glycerine of b. 10%, the glycerine of c. 20%, the glycerine of d. 30%, the glycerine of e 40%.
Specific embodiment：
Below in conjunction with example, the invention will be further described.
Embodiment 1：
Each 10.0g is weighed by Li: Mn=1.10 :The well mixed lithium manganese carbonate mixing of 2.00 molar ratios 5 parts of thing, is placed in crucible, adds the aqueous solution containing glycerine 0.5,1.0,2.0,3.0 and 4.0g, lithium manganese carbonate mixture is stirred Pulp-like is mixed, is then placed in heating burning insulation 1h in the Muffle furnace that constant temperature is 700 DEG C, taking-up, which is positioned in air, to be cooled to Room temperature, obtain final product.The XRD spectrum of its product such as Fig. 1.
Embodiment 2：
Each 10.0g is weighed by Li: Mn=1.05 :The well mixed lithium manganese carbonate mixing of 2.00 molar ratios 5 parts of thing, is placed in crucible, adds the aqueous solution containing glycerine 0.5,1.0,2.0,3.0 and 4.0g, lithium manganese carbonate mixture is stirred Pulp-like is mixed, is then placed in heating burning insulation 1h in the Muffle furnace that constant temperature is 700 DEG C, taking-up, which is positioned in air, to be cooled to Room temperature, obtain final product.The XRD spectrum of its product such as Fig. 1.

Claims (5)

  1. A kind of 1. preparation method of layered lithium manganate material, it is characterised in that：According to Li:Mn=1 ~ 1.30:1.00 weigh Lithium carbonate and manganese carbonate reactant, it is uniform as medium progress ball milling mixing using absolute alcohol, then dry and obtain under temperature 60 C Reactant mixture raw material；The glycerine of reactant mixture raw material gross mass 5 ~ 30% is incorporated as into reactant mixture raw material, and is mixed To close uniformly, be then placed in the Muffle furnace for the preheating constant temperature that temperature is 500 ~ 800 DEG C, the temperature of the preheating constant temperature is 700 DEG C, Combustion reaction is heated under conditions of Muffle furnace closing and is incubated 0.5 ~ 3h, cooling obtains stratiform LiMnO2Material.
  2. 2. preparation method according to claim 1, it is characterised in that the Li:Mn=1.10: 1.00.
  3. 3. preparation method according to claim 1, it is characterised in that the amount that glycerine adds is total for reactant mixture raw material 10 % of quality.
  4. 4. according to the method for claim 1, it is characterised in that the heating combustion reaction is simultaneously incubated 1 ~ 2 h.
  5. 5. according to the method for claim 1, it is characterised in that described to be cooled to cooling air mode.
CN201410800741.8A 2014-12-22 2014-12-22 A kind of preparation method of layered lithium manganate material Expired - Fee Related CN104538589B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410800741.8A CN104538589B (en) 2014-12-22 2014-12-22 A kind of preparation method of layered lithium manganate material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410800741.8A CN104538589B (en) 2014-12-22 2014-12-22 A kind of preparation method of layered lithium manganate material

Publications (2)

Publication Number Publication Date
CN104538589A CN104538589A (en) 2015-04-22
CN104538589B true CN104538589B (en) 2018-03-27

Family

ID=52854085

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410800741.8A Expired - Fee Related CN104538589B (en) 2014-12-22 2014-12-22 A kind of preparation method of layered lithium manganate material

Country Status (1)

Country Link
CN (1) CN104538589B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106299335A (en) * 2015-06-25 2017-01-04 云南民族大学 One prepares LiAl0.04mn1.96o4the method of positive electrode

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1234178C (en) * 2003-05-07 2005-12-28 桂林工学院 Doped lithium nickelate low temperature combustion synthetic method

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Glycerol-assisted solution combustion synthesis of improved LiMn2O4;GUIYANG LIU;《 Materials Science-Poland》;20130829;参见386-387页 *
Synthesis and electrochemical characterization of orthorhombic LiMnO2 material;Y.S. Lee;《Electrochimica Acta》;20030405;第1031-1039页 *
原料对液-固燃烧法合成尖晶型LiMn2O4的影响;郭俊明;《云南民族大学学报》;20110930;参见337-339页 *

Also Published As

Publication number Publication date
CN104538589A (en) 2015-04-22

Similar Documents

Publication Publication Date Title
CN105185954B (en) A kind of LiAlO2Coat LiNi1-xCoxO2Anode material for lithium-ion batteries and preparation method thereof
KR101895641B1 (en) Cathode material and lithium ion battery therefrom
CN101807696A (en) Titanium phosphate lithium material used for cathode of lithium ion battery and preparation method thereof
CN103474656A (en) Preparation method for metal-doped lithium/carbon manganese phosphate composite from manganese phosphate
CN103078106B (en) Method for preparing lithium manganate anode materials of lithium ion battery
CN102956883A (en) AnodePositive electrode material of lithium ion battery with porous laminated structure and preparation method thereof
CN101853936A (en) Method for preparing lithium ion battery cathode material lithium manganese phosphate
CN104112849A (en) Light metal element-doped ternary lithium ion battery positive electrode material and synthesis method thereof
CN105789607A (en) Preparation method of lithium titanate anode material doped with rare earth
CN102447097A (en) Preparation method of lithium ion cathode material nickel manganese cobalt
CN108793254A (en) A kind of Na0.7ZnxMnyO2The preparation method of stratified material
CN100371239C (en) Method for preparing high density lithium ferric phosphate by microwave heating
CN104752711A (en) Preparation method of high-performance nickel doped LiMn2O4 cathode material
CN106981653B (en) Preparation method of nano spinel type nickel-doped lithium manganate material
CN113582253A (en) Quaternary positive electrode material and preparation method and application thereof
CN104538589B (en) A kind of preparation method of layered lithium manganate material
CN101017892A (en) Positive material for the lithium ion battery and preparing method
CN104134794B (en) Lithium-rich manganese-based Layered Lithium cell positive material and preparation method thereof
CN102779992A (en) Lithium ion battery positive electrode material in layer structure and preparation method thereof
CN103151515B (en) A kind of preparation method of niobium cation doping lithium manganate composite anode material
CN105576228A (en) Method for preparing lithium manganate to serve as lithium-ion battery by sol-gel method
CN103794785B (en) A kind of preparation method of lanthanum ferrum nickel cation doping acid lithium-carbon composite anode material
CN105958018A (en) Preparation method for vanadium-doped lithium titanate negative electrode material
CN107565128B (en) Li3Cr(MoO4)3Application in positive electrode of lithium ion battery
CN104538617A (en) One-step method for preparing laminated lithium manganate material

Legal Events

Date Code Title Description
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180327

Termination date: 20191222

CF01 Termination of patent right due to non-payment of annual fee