CN107697953A - A kind of preparation technology of modified lithium manganate - Google Patents
A kind of preparation technology of modified lithium manganate Download PDFInfo
- Publication number
- CN107697953A CN107697953A CN201710964238.XA CN201710964238A CN107697953A CN 107697953 A CN107697953 A CN 107697953A CN 201710964238 A CN201710964238 A CN 201710964238A CN 107697953 A CN107697953 A CN 107697953A
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- Prior art keywords
- acetate
- lithium manganate
- firing chamber
- gel
- modified lithium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1207—Permanganates ([MnO]4-) or manganates ([MnO4]2-)
- C01G45/1214—Permanganates ([MnO]4-) or manganates ([MnO4]2-) containing alkali metals
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
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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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
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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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
Abstract
The present invention relates to a kind of preparation technology of modified lithium manganate, and it includes preparing lithium acetate, chromic acetate, nickel acetate, the mixed solution of manganese acetate, and resorcinol is added into the mixed solution, and stirs, and formalin is added after resorcinol is completely dissolved；Above-mentioned solution is placed in the container of firing chamber upper end again, gel is formed to solution heating response by the heat of firing chamber；Then gel is flowed into the accommodating chamber of firing chamber side, then be dried and sinter to accommodating chamber heat supply, and to above-mentioned gel by the heat supply room of firing chamber's opposite side；The product of sintering is ground again, obtains mixing nickel chromium triangle modified lithium manganate.The present invention can improve the phase purity of product using sintering, improve the crystal property, specific discharge capacity and energy density of material；And by rational raw material proportioning, improve the chemical property of material；The preparation of gel, sintering integrated automated production are realized using container, firing chamber simultaneously, substantially increase production efficiency.
Description
Technical field
The present invention relates to the preparation of manganate cathode material for lithium, specifically a kind of preparation technology of modified lithium manganate.
Background technology
LiMn2O4 with its promoter manganese is abundant, cost is low, security is good, non-environmental-pollution, easily prepare the advantages that turn into power
The first choice of anode material for lithium-ion batteries, but be its property the main reason for the capability of industrialization formation of obstruction electrokinetic cell type LiMn2O4
Can be not sufficiently stable, i.e., its during charge and discharge cycles, capacity attenuation is very fast, be especially apparent under high temperature.Influence its cycle performance
Factor essentially consist in：1st, the purity of phase structure and stability, microscopic appearance are irregular；2nd, the Jahn-Teller of material in itself
Effect；3rd, dissolving of manganese etc. in lithium manganate material.And the major measure for currently suppressing Jahn-Teller deformation be it is bulk phase-doped,
After metal cation substitutes Manganic ion, lattice constant reduces, and structure cell shrinks, and the stability of spinel structure strengthens and made
The oxidation state of manganese is more than 3.55, so as to reach the purpose for suppressing Jahn-Teller deformation.
At present, the main method of synthetic lithium manganate can be divided into two kinds of solid phase method and liquid phase method.Liquid phase method such as sol-gal process,
This method is widely used in the preparation of nano-ceramic powder, film and fiber coat.Because this method can realize the atom of reactant
Level uniformly mixing, and synthesis temperature is low, thus the particle diameter for preparing product is mostly nanoscale, and homogeneity is good, specific surface area is big, shape
State and composition are easily controllable.Existing sol-gal process principle is that various metals cation can form chelate with organic acid, should
Chelate can polymerize with polyhydroxy-acid, so as to form the equally distributed solid polymer precursor of cation, under vacuum
Precursor is heat-treated and can obtain final product；But this method preparation time is grown, complex process, vacuum heat treatment process
Unmanageable, cost is higher.
Generally, the output voltage of dynamical lithium-ion battery packs between 300-400V, it is necessary to which a large amount of monocell is gone here and there
Connection, the number of series-connected cell depend on monocell operating voltage, and single battery voltage is higher, and Series Sheet number of batteries is fewer, related
Control circuit is simpler, and the reliability and security of integral battery door group are higher, and the operating voltage of lithium ion battery depends on just
The voltage of pole material.The thus doping vario-property of lithium manganate having spinel structure positive electrode, has to the positive electrode for preparing high potential
Significance.This existing preparation technology is complicated, cost is high, automaticity is relatively low.
The content of the invention
For above-mentioned technical problem, the present invention provides a kind of preparation technology for the modified lithium manganate for improving production efficiency.
Technical scheme is used by the present invention solves above-mentioned technical problem：A kind of preparation technology of modified lithium manganate, its
Using the following steps：
（1）Lithium acetate, chromic acetate, nickel acetate, the mixed solution of manganese acetate are prepared, resorcinol is added into the mixed solution,
And stir, add formalin after resorcinol is completely dissolved；
（2）Above-mentioned solution is placed in the container of firing chamber upper end, solution heating response formed again by the heat of firing chamber
Gel；
（3）Then the sealing plate of container bottom is opened, gel is flowed into the accommodating chamber of firing chamber side, then it is another by firing chamber
The heat supply room of side is dried and sintered to accommodating chamber heat supply, and to above-mentioned gel；
（4）The product of sintering is ground again, obtains mixing nickel chromium triangle modified lithium manganate.
Preferably, the lithium acetate：Chromic acetate：Nickel acetate：Manganese acetate：Resorcinol：The mol ratio of formaldehyde is 1：
0.2:0.4：1.4：（3--7）：（7-8）.
Preferably, be 50-70 DEG C to solution heating-up temperature, reaction time 10--14h.
Preferably, the firing chamber is separated into left and right two spaces by heat-conducting plate, one of space is the heat supply
Room, another space are the accommodating chamber.
Preferably, the heat-conducting plate is formed using the upper, middle and lower segment folded plate for forming two bendings, wherein upper folded plate
Rolled tiltedly to accommodating chamber with lower flap portion, middle folded plate rolls oblique to heat supply room.
Preferably, the container is arranged on the upside of the accommodating chamber.
As can be known from the above technical solutions, the present invention is with lithium acetate, chromic acetate, manganese acetate, nickel acetate, resorcinol, formaldehyde
Modified lithium manganate is prepared for raw material, the phase purity of product can be improved using sintering therebetween, improves crystal property, the electric discharge ratio of material
Capacity and energy density；And by rational raw material proportioning, improve the chemical property of material；Simultaneously using container, roasting
The preparation of gel, sintering integrated automated production are realized in room, substantially increase production efficiency.
Embodiment
The present invention is described in detail below, illustrative examples of the invention and explanation are used for explaining the present invention herein, but
It is not as a limitation of the invention.
A kind of preparation technology of modified lithium manganate, it uses the following steps：
First, lithium acetate, chromic acetate, nickel acetate, manganese acetate mixed solution are prepared, resorcinol is added into the mixed solution,
And stir, add formalin after resorcinol is completely dissolved；Because the pairing of raw material has to the structure and electrical property of material
Large effect, the present invention use lithium acetate：Chromic acetate：Nickel acetate：Manganese acetate：Resorcinol：The mol ratio of formaldehyde is 1：
0.2:0.4：:1.4：（3--7）：（7-8）, this proportioning can ensure lithium manganate material crystal property, phase purity, particle diameter, dispersiveness
Reach preferred with homogeneity.
Above-mentioned solution is placed in the container of firing chamber upper end, solution heating response formed again by the heat of firing chamber
Gel；It it is 50-70 DEG C, reaction time 10--14h to solution heating-up temperature, so that raw material is abundant in implementation process
Reaction.The present invention can carry out heating response using the waste heat of firing chamber to solution, can reduce cost；Temperature control can be coordinated to fill simultaneously
Put, solution is reacted with specified temperature.
Then the sealing plate of container bottom is opened, gel is flowed into the accommodating chamber of firing chamber side, realizes prepared by gel
Integration production automatically with roasting, then entered by the heat supply room of firing chamber's opposite side to accommodating chamber heat supply, and to above-mentioned gel
Row is dried and sintering, and thus, the present invention is calcined using one realizes the holding of gel, dries and sintering, its is simple in construction, into
This is relatively low.Preferably, the firing chamber is separated into left and right two spaces by heat-conducting plate, one of space is the heat supply
Room, another space are the accommodating chamber, and the heat-conducting plate is formed using the upper, middle and lower segment folded plate for forming two bendings, its
In upper folded plate and lower flap portion rolled to accommodating chamber oblique, middle folded plate rolls oblique to heat supply room.The lower flap portion so set causes it
Corresponding heat supply room forms the conical region that lower end is small, upper end is big, is advantageous to heat importing accommodating chamber；In so setting
Folded plate causes its corresponding accommodating chamber to form the conical region that lower end is small, upper end is big, is advantageous to hold gel, while inclined
Middle folded plate, facilitate heat supply room to heat, heating effect can be improved；The upper folded plate so set is advantageous to the gas discharge of heat supply room,
Also the steam for being advantageously used for accommodating chamber is collected and outer row.
In implementation process, the container is arranged on the upside of the accommodating chamber, caused by gel preparation course
Steam heats to container, is on the one hand advantageous to control heating-up temperature, another aspect instant gelatine flows into accommodating chamber, while real
Prepared by existing gel, the consecutive production of roasting, improves production efficiency.Finally the product of sintering is ground, obtains mixing nickel
Chromium modified lithium manganate.To analyze after testing, upper this mixes the first discharge specific capacity of chromium nickel modified lithium manganate up to more than 110mAh/g,
Capability retention is more than 90% after circulating 100 times, and other indexs meet the standard of cell positive material.And the technique is with showing
There is routine techniques technique to improve 20-30% compared to production efficiency.
Above-mentioned embodiment is used for illustrative purposes only, and is not limitation of the present invention, relevant technical field
Those of ordinary skill, can be so that various changes can be made and modification without departing from the spirit and scope of the present invention, therefore institute
There is equivalent technical scheme also to belong to scope of the invention.
Claims (6)
1. a kind of preparation technology of modified lithium manganate, it uses the following steps：
（1）Lithium acetate, chromic acetate, nickel acetate, the mixed solution of manganese acetate are prepared, resorcinol is added into the mixed solution,
And stir, add formalin after resorcinol is completely dissolved；
（2）Above-mentioned solution is placed in the container of firing chamber upper end, solution heating response formed again by the heat of firing chamber
Gel；
（3）Then the sealing plate of container bottom is opened, gel is flowed into the accommodating chamber of firing chamber side, then it is another by firing chamber
The heat supply room of side is dried and sintered to accommodating chamber heat supply, and to above-mentioned gel；
（4）The product of sintering is ground again, obtains mixing nickel chromium triangle modified lithium manganate.
2. the preparation technology of modified lithium manganate according to claim 1, it is characterised in that：The lithium acetate：Chromic acetate：Acetic acid
Nickel：Manganese acetate：Resorcinol：The mol ratio of formaldehyde is 1：0.2:0.4：1.4：（3--7）：（7-8）.
3. the preparation technology of modified lithium manganate according to claim 1, it is characterised in that：It is 50-70 to solution heating-up temperature
DEG C, reaction time 10--14h.
4. the preparation technology of modified lithium manganate according to claim 1, it is characterised in that：The firing chamber is separated by heat-conducting plate
Into left and right two spaces, one of space is the heat supply room, and another space is the accommodating chamber.
5. the preparation technology of modified lithium manganate according to claim 4, it is characterised in that：The heat-conducting plate uses and forms two
The upper, middle and lower segment folded plate of bending is formed, wherein upper folded plate and lower flap portion roll oblique to accommodating chamber, middle folded plate is to heat supply room
Roll oblique.
6. the preparation technology of modified lithium manganate according to claim 1, it is characterised in that：The container is arranged on the receiving
On the upside of room.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710964238.XA CN107697953A (en) | 2017-10-19 | 2017-10-19 | A kind of preparation technology of modified lithium manganate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710964238.XA CN107697953A (en) | 2017-10-19 | 2017-10-19 | A kind of preparation technology of modified lithium manganate |
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| CN107697953A true CN107697953A (en) | 2018-02-16 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI788041B (en) * | 2021-10-05 | 2022-12-21 | 芯量科技股份有限公司 | Battery positive electrode material and manufacturing method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104319400A (en) * | 2014-10-11 | 2015-01-28 | 柳州豪祥特科技有限公司 | Preparation method of nano spinel-type lithium manganate |
| CN104319399A (en) * | 2014-10-11 | 2015-01-28 | 柳州豪祥特科技有限公司 | Preparation method of modified nickel-doped lithium manganate |
| CN104393276A (en) * | 2014-10-11 | 2015-03-04 | 柳州豪祥特科技有限公司 | Preparation method of doping-modified spinel-type lithium manganate |
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2017
- 2017-10-19 CN CN201710964238.XA patent/CN107697953A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104319400A (en) * | 2014-10-11 | 2015-01-28 | 柳州豪祥特科技有限公司 | Preparation method of nano spinel-type lithium manganate |
| CN104319399A (en) * | 2014-10-11 | 2015-01-28 | 柳州豪祥特科技有限公司 | Preparation method of modified nickel-doped lithium manganate |
| CN104393276A (en) * | 2014-10-11 | 2015-03-04 | 柳州豪祥特科技有限公司 | Preparation method of doping-modified spinel-type lithium manganate |
Non-Patent Citations (1)
| Title |
|---|
| 汪仁宏等: "《企业节能使用手册》", 30 June 1997, 东南大学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI788041B (en) * | 2021-10-05 | 2022-12-21 | 芯量科技股份有限公司 | Battery positive electrode material and manufacturing method thereof |
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Application publication date: 20180216 |