CN109279657A - A kind of production method of lithium manganate battery material - Google Patents
A kind of production method of lithium manganate battery material Download PDFInfo
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- CN109279657A CN109279657A CN201811084603.9A CN201811084603A CN109279657A CN 109279657 A CN109279657 A CN 109279657A CN 201811084603 A CN201811084603 A CN 201811084603A CN 109279657 A CN109279657 A CN 109279657A
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- Prior art keywords
- production method
- lithium
- lithium manganate
- manganate battery
- sintering
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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
-
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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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
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- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of production methods of lithium manganate battery material, mainly including the following steps: mixing, crushing and classification, is repeatedly sintered, cools down and pulverize and sieve pre-burning.Present invention solves the technical problem that being to overcome the LiMn2O4 production method method preparation time of the prior art long, complex process, higher cost, production efficiency is low, and the defect that impurity content is high, provides a kind of production method of lithium manganate battery material.The features such as a kind of production method of lithium manganate battery material has preparation process simple, and high production efficiency is at low cost, and resulting LiMn2O4 is with high purity.
Description
Technical field
The present invention relates to production of energy technical field, specially a kind of production method of lithium manganate battery material.
Background technique
It by lithium metal or lithium alloy is negative electrode material that lithium battery, which is a kind of, and uses the battery of non-aqueous electrolytic solution.By
It is very active in the chemical characteristic of lithium metal, so that the processing of lithium metal, preservation, use, very high to environmental requirement, therefore lithium
Battery is not applied for a long time.With the development of science and technology, present lithium battery has been increasingly becoming mainstream.Lithium battery is big
Cause can be divided into two class of lithium metal battery and lithium ion battery, and lithium metal battery is usually to use manganese dioxide for positive electrode, gold
Belong to lithium or its alloying metal is negative electrode material, using the battery of non-aqueous electrolytic solution, and lithium ion battery is usually to use lithium
Alloying metal oxide is positive electrode, and graphite is negative electrode material, uses the battery of nonaqueous electrolyte.
Lithium manganate battery refers to that anode uses the battery of lithium manganate material, its nominal voltage of lithium manganate battery 2.5~
4.2v, since its is at low cost, safety is good to be thus widely used.Production lithium manganate battery needs to use LiMn2O4, LiMn2O4
Predominantly lithium manganate having spinel structure, it is excellent that it as electrode material has that price is low, current potential is high, environmental-friendly, security performance is high etc.
Point.There are many kinds of the synthetic methods of lithium manganate having spinel structure, mainly there is high temperature solid-state method, melt impregnation, microwave process for synthesizing, molten
Sol-gel, emulsification seasoning, coprecipitation, Pechini method and hydrothermal synthesis method etc., but existing LiMn2O4 producer
Method preparation time is long, complex process, higher cost, and production efficiency is low and impurity content is high.
Summary of the invention
Present invention solves the technical problem that it is to overcome the LiMn2O4 production method method preparation time of the prior art long, technique
Complexity, higher cost, production efficiency is low, and the defect that impurity content is high, provides a kind of producer of lithium manganate battery material
Method.A kind of production method of lithium manganate battery material has preparation process simple, and high production efficiency is at low cost, and institute
The features such as LiMn2O4 obtained is with high purity.
To achieve the above object, the invention provides the following technical scheme: a kind of production method of lithium manganate battery material, packet
Include following steps:
A, mixing: electrolytic manganese dioxide and lithium-containing compound are chosen, using dry mixed, wherein electrolytic manganese dioxide with
Lithium-containing compound is that 2:1 carries out proportion mixing with the molar ratio of Mn:Li, is sufficiently mixed uniform raw material, mixing to obtain
It needs to mix certain lithium fluoride in the process to provide F doping；
B, pre-burning: being put into rotary kiln and be passed through nitrogen for the raw material mixed, carries out preheating to mixture, in advance
It needs that the additive for promoting grain growth is added during burning；
C, crushing and classification: the bulk mixture that pre-burning is completed is put into disintegrating apparatus and carries out pulverization process, makes its volume
Become smaller, and smashed mixture is divided by≤50g/cm according to the size of size3, 50~100g/cm3, > 100g/cm3Three
Grade；
D, repeatedly sintering: crushing and classification treated mixture is carried out repeatedly and prolonged sintering, to guarantee crystal
Structural integrity, to form large-particle monocrystal LiMn2O4；
E, cooling: material is taken out after the completion of sintering and carries out natural cooling, its temperature is made to be down to room temperature；
F, it pulverizes and sieves: air-flow break process is carried out to material after cooling, then electromagnetism utilizes sieve all over rear except iron is several
Net sieves material, and finally carrying out vacuum packaging can be obtained finished product.
Preferably, mixing amount should be controlled in 150~200kg, 60~80min of mixing time in the step A, and revolving speed 0~
25m/min。
Preferably, the kiln temperature in the step B should control 525 DEG C~575 DEG C~between, burn-in time 1
~1.5 hours.
Preferably, the temperature fluctuation amplitude in the step D in sintering furnace should control within 5 DEG C, it is ensured that once sintered
Temperature meets 750 DEG C~850 DEG C, 700 DEG C~800 DEG C of double sintering temperature satisfaction, and each sintering time is not less than 1 hour.
Preferably, the number that electromagnetism removes iron in the step F is no less than three times, and the mesh number of sieve is 200~250.
Compared with prior art, the beneficial effects of the present invention are:
1, preparation process is simple.
2, high production efficiency.
3, it economizes on resources and material cost.
4, resulting LiMn2O4 purity is high, the lithium manganese oxide content of other miscellaneous phases is low, content < 0.1%.
Detailed description of the invention
Fig. 1 is production method flow chart of the invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Referring to Fig. 1, the present invention provides a kind of technical solution: a kind of production method of lithium manganate battery material, including with
Lower step:
A, mixing: electrolytic manganese dioxide and lithium-containing compound are chosen, using dry mixed, wherein electrolytic manganese dioxide with
Lithium-containing compound is that 2:1 carries out proportion mixing with the molar ratio of Mn:Li, is sufficiently mixed uniform raw material, mixing to obtain
Amount, which should be controlled, to be needed to mix centainly in 150~200kg, 60~80min of mixing time, 0~25m/min of revolving speed, mixing process
Lithium fluoride needs the lithium salts of excessive addition during mixing to provide F doping to guarantee that sintered product is rich lithium；
B, pre-burning: being put into rotary kiln and be passed through nitrogen for the raw material mixed, carries out preheating to mixture, returns
Rotary Kiln Temperature should control 525 DEG C~575 DEG C~between, burn-in time be 1~1.5 hour, needed during pre-burning be added promote
Into the additive of grain growth, so that the pattern and grain size of product can be reconciled during the sintering process；
C, crushing and classification: the bulk mixture that pre-burning is completed is put into disintegrating apparatus and carries out pulverization process, makes its volume
Become smaller, and smashed mixture is divided by≤50g/cm according to the size of size3, 50~100g/cm3, > 100g/cm3Three
Grade；
D, repeatedly sintering: crushing and classification treated mixture is carried out repeatedly and prolonged sintering, to guarantee crystal
Structural integrity, to form large-particle monocrystal LiMn2O4, the temperature fluctuation amplitude in sintering furnace should be controlled within 5 DEG C, and
Ensure that once sintered temperature meets 750 DEG C~850 DEG C, 700 DEG C~800 DEG C of double sintering temperature satisfaction, each sintering time is not
Lower than 1 hour；
E, cooling: material is taken out after the completion of sintering and carries out natural cooling, its temperature is made to be down to room temperature；
F, it pulverizes and sieves: air-flow break process is carried out to material after cooling, then electromagnetism utilizes sieve all over rear except iron is several
Net sieves material, and electromagnetism is no less than three times except the number of iron, and the mesh number of sieve is 200~250, finally carries out vacuum
Finished product can be obtained in packaging.
Contrived experiment:
Embodiment 1: taking mixing amount is 150kg, mixing time 60min, and revolving speed control carries out in fact in 10m/min
It tests, the lithium fluoride of 100ml is filled in mixing process to provide F doping, and add the lithium salts of 1.5L during mixing, with
Guarantee that sintered product is rich lithium, mixture is put into rotary kiln carries out pre-burning later, the temperature control of rotary kiln exists
525 DEG C, burn-in time is 1 hour, needs that the additive for promoting grain growth is added during pre-burning, so as to during the sintering process
The pattern and grain size of product can be reconciled, the bulk mixture that pre-burning is completed is put into disintegrating apparatus crushes later
Pulverizer can be selected in processing, disintegrating apparatus, by external power supply and switch driving motor, so that pulverizer operates, thus to mixed
It closes material and carries out pulverization process, and make volume≤50g/cm of mixture3, then repeatedly it is sintered, to guarantee crystal structure
Completely, to form large-particle monocrystal LiMn2O4, it is 750 DEG C that once sintered temperature is repeatedly made when sintering, double sintering
Temperature is 700 DEG C, and the two-step sintering time is respectively 1.5 hours and 2 hours, and material to be mixed is crushed after being cooled to room temperature later
Sieving processing, is powered to generate magnetic field to electromagnet, to remove iron tramp contained in mixture, whole process is repeated
Three times, sieving processing finally is carried out to mixture using the sieve that mesh number is 200~250, so that required finished product is obtained, this reality
Example is applied after experiment, measuring resulting finished product efficiency for charge-discharge is 152.734%, specific discharge capacity 84.723, charging
Specific capacity is 129.400, reversible capacity 100, and 500 or more cyclicity keeps about 80% capacity.
Embodiment 2: taking mixing amount is 200kg, mixing time 80min, and revolving speed control carries out in fact in 25m/min
It tests, the lithium fluoride of 100ml is filled in mixing process to provide F doping, and add the lithium salts of 1.5L during mixing, with
Guarantee that sintered product is rich lithium, mixture is put into rotary kiln carries out pre-burning later, the temperature control of rotary kiln exists
575 DEG C, burn-in time is 1.5 hours, needs that the additive for promoting grain growth is added during pre-burning, so as in sintering process
In can reconcile the pattern and grain size of product, the bulk mixture that pre-burning is completed is put into disintegrating apparatus carries out powder later
Pulverizer can be selected in broken processing, disintegrating apparatus, by external power supply and switch driving motor, so that pulverizer operates, thus right
Mixture carries out pulverization process, and makes the volume > 100g/cm of mixture3, then repeatedly it is sintered, to guarantee crystal structure
Completely, to form large-particle monocrystal LiMn2O4, it is 850 DEG C that once sintered temperature is repeatedly made when sintering, double sintering
Temperature is 750 DEG C, and the two-step sintering time is respectively 1.5 hours and 2 hours, and material to be mixed is crushed after being cooled to room temperature later
Sieving processing, is powered to generate magnetic field to electromagnet, to remove iron tramp contained in mixture, whole process is repeated
Three times, sieving processing finally is carried out to mixture using the sieve that mesh number is 200~250, so that required finished product is obtained, this reality
Example is applied after experiment, measuring resulting finished product efficiency for charge-discharge is 403.979%, specific discharge capacity 40.720, charging
Specific capacity is 164.501, reversible capacity 115, and 500 or more cyclicity keeps about 90% capacity.
Compared with prior art, the beneficial effects of the present invention are:
1, preparation process is simple.
2, high production efficiency.
3, it economizes on resources and material cost.
4, resulting LiMn2O4 purity is high, the lithium manganese oxide content of other miscellaneous phases is low, content < 0.1%.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (5)
1. a kind of production method of lithium manganate battery material, which comprises the following steps:
A, mixing: electrolytic manganese dioxide and lithium-containing compound are chosen, using dry mixed, wherein electrolytic manganese dioxide with contain lithium
Compound is that 2:1 carries out proportion mixing with the molar ratio of Mn:Li, is sufficiently mixed uniform raw material, mixing process to obtain
It is middle to mix certain lithium fluoride to provide F doping；
B, pre-burning: being put into rotary kiln and be passed through nitrogen for the raw material mixed, carries out preheating to mixture, pre-burning
It needs that the additive for promoting grain growth is added in the process；
C, crushing and classification: the bulk mixture that pre-burning is completed being put into disintegrating apparatus and carries out pulverization process, its volume is made to become smaller,
And smashed mixture is divided by≤50g/cm according to the size of size3, 50~100g/cm3, > 100g/cm3Three grades；
D, repeatedly sintering: crushing and classification treated mixture is carried out repeatedly and prolonged sintering, to guarantee crystal structure
Completely, to form large-particle monocrystal LiMn2O4；
E, cooling: material is taken out after the completion of sintering and carries out natural cooling, its temperature is made to be down to room temperature；
F, it pulverizes and sieves: air-flow break process is carried out to material after cooling, then electromagnetism utilizes sieve pair all over rear except iron is several
Material is sieved, and finally carrying out vacuum packaging can be obtained finished product.
2. a kind of production method of lithium manganate battery material according to claim 1, it is characterised in that: in the step A
Mixing amount should be controlled in 150~200kg, 60~80min of mixing time, 0~25m/min of revolving speed.
3. a kind of production method of lithium manganate battery material according to claim 1, it is characterised in that: in the step B
Kiln temperature should control 525 DEG C~575 DEG C~between, burn-in time be 1~1.5 hour.
4. a kind of production method of lithium manganate battery material according to claim 1, it is characterised in that: in the step D
Temperature fluctuation amplitude in sintering furnace should control within 5 DEG C, it is ensured that once sintered temperature meets 750 DEG C~850 DEG C, secondary burning
Junction temperature meets 700 DEG C~800 DEG C, and each sintering time is not less than 1 hour.
5. a kind of production method of lithium manganate battery material according to claim 1, it is characterised in that: in the step F
Electromagnetism is no less than three times except the number of iron, and the mesh number of sieve is 200~250.
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| CN201811084603.9A CN109279657A (en) | 2018-09-17 | 2018-09-17 | A kind of production method of lithium manganate battery material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109768268A (en) * | 2019-03-16 | 2019-05-17 | 湖南海利锂电科技股份有限公司 | Manganate cathode material for lithium and preparation method thereof |
| CN110635130A (en) * | 2019-09-11 | 2019-12-31 | 湖南金富力新能源股份有限公司 | Spherical or spheroidal lithium manganate positive electrode material and preparation method and application thereof |
| CN110970615A (en) * | 2019-06-11 | 2020-04-07 | 青岛红星新能源技术有限公司 | Modification method of high-performance lithium manganate positive electrode material |
-
2018
- 2018-09-17 CN CN201811084603.9A patent/CN109279657A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109768268A (en) * | 2019-03-16 | 2019-05-17 | 湖南海利锂电科技股份有限公司 | Manganate cathode material for lithium and preparation method thereof |
| CN110970615A (en) * | 2019-06-11 | 2020-04-07 | 青岛红星新能源技术有限公司 | Modification method of high-performance lithium manganate positive electrode material |
| CN110635130A (en) * | 2019-09-11 | 2019-12-31 | 湖南金富力新能源股份有限公司 | Spherical or spheroidal lithium manganate positive electrode material and preparation method and application thereof |
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Application publication date: 20190129 |