CN102214820A - Industrial preparation method for multielement-coated lithium manganese oxide material - Google Patents
Industrial preparation method for multielement-coated lithium manganese oxide material Download PDFInfo
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Abstract
The invention discloses an industrial preparation method for a multielement-coated lithium manganese oxide material. The method comprises the following steps of: adding microwave-absorbing medium and metal or metalloid compounds which are used as microwave-absorbing and coating raw materials into a lithium manganese oxide raw material; mixing; performing ball milling; putting into an industrial microwave stove which is specially designed and manufactured, wherein the temperature of reacting materials and the microwave heating time are strictly controlled; and after sintering is finished, pulverizing, screening and packaging the products. The method is simple; by using the microwave-absorbing medium, the interior and the exterior of the reacting materials are heated quickly at the same time, so that the quick microwave sintering in a real sense is realized; and the preparation process is high in efficiency, low in cost and beneficial to the industrial production. A lithium ion battery made of the cathode material obtained by the method is extremely applicable to electricity storage equipment in the fields of mobile phones, laptops, small cameras, electric automobiles, satellites, spaceflights and military affairs.
Description
Technical field
The present invention relates to a kind of industrialization production method of polynary coating lithium manganese oxide material, belong to the electrochemical power source technical field of material.
Background technology
Lithium ion battery is as the green high-capacity battery, numerous advantages such as have that voltage height, energy density are big, good cycle, self discharge are little, memory-less effect, operating temperature range are wide are widely used in the portable electric appts such as mobile phone, laptop computer, miniature camera.Lithium ion battery also will be widely used in electric automobile, satellite, space flight and military field as energy and material of new generation.Positive electrode is the important component part of lithium-ion-power cell, researches and develops the key point that high performance positive electrode has become the lithium ion battery development.Lithium ion cell anode material lithium cobaltate (LiCoO
2), lithium nickelate (LiNiO2), spinel lithium manganate (LiMn2O4), nickel ternary cobalt manganese lithium use on small-scale lithium ion cell.Cobalt acid lithium (LiCoO
2), lithium nickelate (LiNiO2) costs an arm and a leg and stability and poor stability because of using strategic resource, all not too is fit to the battery that is used as power.LiMn2O4 aboundresources cost is low, particularly updates aspect the high temperature cyclic performance at cycle performance, promises to be the electrokinetic cell novel anode material most.
The method for preparing at present lithium manganate material has solid-phase synthesis, sol-gel process, oxidation-reduction method and hydro thermal method etc.The advantage of sol-gel method is precursor solution chemical uniformity good (can reach the molecular level level), but dry the contraction greatly, synthesis cycle is longer, and the suitability for industrialized production difficulty is bigger.What suitability for industrialized production generally adopted at present is solid-phase sintering method, because the thermal conductivity of this material is bad, so sintering time long (sintering time was greater than 20 hours), power consumption is big, production efficiency is low, and the material inequality of being heated in sintering furnace causes the material consistent appearance poor, and material granule has unusual increase phenomenon, thereby influences the chemical property of material.Though both at home and abroad the report of useful microwave method synthesizing lithium ion battery material all rests on the laboratory research stage, because of lacking suction ripple medium, can not the fast Absorption microwave radiation energy, heats is relatively poor, and technology is immature, is difficult to carry out suitability for industrialized production.
Summary of the invention
The present invention seeks to overcome prior art lithium manganese oxide anode material cost height, energy consumption is big, yield poorly, the shortcoming of poor performance, a kind of industrialization production method of polynary coating lithium manganese oxide material is provided, this method is to add the microwave radiation absorbing medium and metal (or metalloid) compound involves the coating raw material as suction in the lithium manganese oxide raw material, batching is after stirring ball-milling, reinstall in the industrial microwave oven of particular design manufacturing, automatically import quantitative gas or vacuumize unlatching microwave source, the temperature and the microwave heating time of strict control reaction mass, after sintering is finished, will pack behind the material crushing screening.The particular design industrial microwave oven is a radiation heating, with infrared or thermocouple temperature measurement, automatically regulate microwave output power strict control sintering temperature and heating time,, make solid phase reaction take place rapidly because the microwave radiation absorbing medium can the fast Absorption microwave radiation energy; The product cost that this industrialization production method is produced is low, and energy consumption is little, the output height, and performance is good, is fit to very much do lithium ion power battery cathode material.
The industrialization production method of polynary coating lithium manganese oxide material of the present invention follows these steps to carry out:
(1) Li source compound and manganese source raw material, microwave radiation absorbing medium, clad metal or metal compound are prepared burden according to element mol ratio Li: Mn: R: M=0.6～1.6: 0.8～2: 0～0.05: 0～0.6, R is the microwave radiation absorbing medium, and M is clad metal or metal compound;
(2) confected materials is packed into behind stirring ball-milling in the industrial microwave oven that particular design makes, automatic ration input gas or vacuumize, controlled microwave source power, microwave sintering temperature are at the 400-1000 degree, and sintering time is 3-400 minute;
(3) the intact synthesis material that takes out of sintering promptly obtains polynary coating lithium manganese oxide material through crushing and classification;
(4) microwave sintering process can be a step sintering process, also can be the multistep sintering process.
Described Li source compound can be a lithium carbonate, lithium dihydrogen phosphate, lithium sulfate, lithium nitrate, lithium hydroxide, lithium acetate, wherein one or more of lithium oxalate, described manganese source raw material can be a manganese dioxide, mangano-manganic oxide, manganese sesquioxide managnic oxide, manganese oxalate, manganese sulfate, manganese carbonate, wherein one or more of manganese nitrate, described R microwave radiation absorbing medium is a superfine iron carbonyl powder, reduced iron powder, lithium hydroxide, ferric sulfate, ferric nitrate, ferrous oxalate, magnesium hydroxide, wherein one or more of aluminium chloride, described M clad metal or metal compound are Ti, Mg, V, Nb, Na, AI, Fe, W, Ni, Mo, Cr, wherein one or more of Si.
Described industrial microwave oven can be box type furnace or continuous tunnel furnace, and described gas is inert gas or oxygen, the vacuum degree of described vacuum≤-0.06Mpa, described microwave source can be three-dimensional multi-source or the single source of evenly arranging, can be fixing generation source or rotate the generation source.
Described microwave multistep sintering process, be after first sintering is intact, in material, add mass ratio again and be 0～0.6% clad metal (or metalloid) compound, add after stirring ball-milling, the sintering in the industrial microwave oven of packing into once more perhaps repeatedly repeats the ball milling sintering process to the material behind the second time microwave sintering again.
The present invention and existing sintering method have following outstanding advantage to comparing:
1. adopt the microwave radiation absorbing medium, the inside and outside while of reaction mass is heated fast, realize microwave sintering truly.
2. the temperature gradient that does not have the normal sintering method to occur, the material consistency that sintering obtains is fine, has characteristics such as crystallite size narrow distribution range, crystal grain are evenly distributed.
3. the short power consumption of microwave sintering time is low, can save time more than 96% than normal sintering, and production efficiency increases substantially, and electricity consumption can be saved more than 97% than normal sintering, and is significantly energy-saving and cost-reducing, reduces manufacturing cost greatly.
4. product has higher tap density, can improve the volume of battery specific capacity greatly.
5. technology is simple, is beneficial to suitability for industrialized production.
6. be highly suitable in low cost, high safety, the high-capacity lithium-ion power battery and use.Characteristics such as make lithium-ion-power cell, have the capacity height, high low temperature has extended cycle life, and security performance is good can be widely used in mobile phone, laptop computer, miniature camera, electric automobile, satellite, space flight and military field.
Embodiment
Embodiment 1
With lithium carbonate, manganese dioxide, ultra-fine reduced iron powder (microwave radiation absorbing medium), aluminium chloride, tungstic acid, molybdenum oxide (particles cladded by metallic compound) are as raw material, according to mol ratio: Li: Mn: Fe: AI: W: Mo=1.03: 2: 0.02: 0.02: 0.01: 0.01 batching, pack into ball grinder stirring ball-milling 4 hours reinstalls in the industrial microwave oven that particular design makes.Automatically the quantitative air of input is opened microwave source, and the temperature of control reaction mass is warmed up to 760 ℃ of insulations 40 minutes again 460 ℃ of pre-burnings 10 minutes, closes microwave source cooling material, material is taken out crushing screening obtain polynary coating lithium manganese oxide material.
Embodiment 2
With lithium carbonate, manganese dioxide, superfine iron carbonyl powder (microwave radiation absorbing medium) magnesium oxide (particles cladded by metallic compound) is as raw material, according to mol ratio: Li: Mn: Fe: Mg=1.1: 1.92: 0.03: 0.02 batchings, pack into ball grinder stirring ball-milling 6 hours, reinstall in the industrial microwave oven of particular design manufacturing, sealing door, automatic vacuum, open microwave source, the temperature of control reaction mass, be warmed up to 760 ℃ of insulations 40 minutes, close microwave source cooling material, material taken out to add mass ratio in material again be 0.3% coating metal compound Si, add after stirring ball-milling sintering in the industrial microwave oven of packing into once more, microwave is warmed up to 700 ℃ of insulations 20 minutes, material is taken out crushing screening obtain polynary coating lithium manganese oxide material.
Embodiment 3
With lithium carbonate, manganese dioxide, aluminium chloride (microwave radiation absorbing medium) magnesium oxide (particles cladded by metallic compound) as raw material, according to mol ratio: Li: Mn: AI: Mg=1.06: 1.9: 0.03: 0.02 batchings, pack into ball grinder stirring ball-milling 7 hours, reinstall in the industrial microwave oven of particular design manufacturing, open microwave source, the temperature of control reaction mass is warmed up to 790 ℃ of insulations 20 minutes, closes microwave source cooling material.Material taken out to add mass ratio in material again be 0.4% particles cladded by metallic compound Cr, add after stirring ball-milling, the interior sintering of the industrial microwave oven of packing into once more, be warmed up to 790 ℃ of insulations 20 minutes, close microwave source, take out through stirring ball-milling material cooling back, the interior sintering of the industrial microwave oven of packing into once more, be warmed up to 700 ℃ of insulations 20 minutes, close microwave source, material is taken out crushing screening obtain polynary coating lithium manganese oxide material.
Claims (6)
1. the industrialization production method of a polynary coating lithium manganese oxide material is characterized in that:
(1) Li source compound and manganese source raw material, microwave absorbing medium, clad metal or metal compound are prepared burden according to element mol ratio Li: Mn: R: M=0.6～1.6: 0.8～2: 0～0.05: 0～0.6, R is the microwave absorbing medium, and M is clad metal or metal compound;
(2) confected materials is packed into behind stirring ball-milling in the industrial microwave oven that particular design makes, automatic ration input gas or vacuumize, controlled microwave source power, microwave sintering temperature are at the 400-1000 degree, and sintering time is 3-400 minute;
(3) the intact synthesis material that takes out of sintering promptly obtains polynary coating lithium manganese oxide material through crushing and classification;
(4) microwave sintering process can be a step sintering process, also can be the multistep sintering process.
2. the industrialization production method of polynary coating lithium manganese oxide material according to claim 1, it is characterized in that: described Li source compound can be a lithium carbonate, lithium dihydrogen phosphate, lithium sulfate, lithium nitrate, lithium hydroxide, lithium acetate, wherein one or more of lithium oxalate, described manganese source raw material can be a manganese dioxide, mangano-manganic oxide, manganese sesquioxide managnic oxide, manganese oxalate, manganese sulfate, manganese carbonate, wherein one or more of manganese nitrate, described R microwave absorbing medium is a superfine iron carbonyl powder, reduced iron powder, lithium hydroxide, ferric sulfate, ferric nitrate, ferrous oxalate, magnesium hydroxide, wherein one or more of aluminium chloride, described M clad metal or metal compound are Ti, Mg, V, Nb, Na, AI, Fe, W, Ni, Mo, Cr, wherein one or more of Si.
3. the industrialization production method of polynary coating lithium manganese oxide material according to claim 1 is characterized in that: described industrial microwave oven can be box type furnace or continuous tunnel furnace.
4. the industrialization production method of polynary coating lithium manganese oxide material according to claim 1 is characterized in that: described gas is inert gas or oxygen, the vacuum degree of described vacuum≤-0.06Mpa.
5. the industrialization production method of polynary coating lithium manganese oxide material according to claim 1 is characterized in that: described microwave source can be three-dimensional multi-source or the single source of evenly arranging, can be fixing generation source or rotate the generation source.
6. the industrialization production method of polynary coating lithium manganese oxide material according to claim 1, it is characterized in that: described microwave multistep sintering process, be after first sintering is intact, adding mass ratio in material again is 0～0.6% clad metal (or metalloid) compound, add after stirring ball-milling, the sintering in the industrial microwave oven of packing into once more perhaps repeatedly repeats the ball milling sintering process to the material behind the second time microwave sintering again.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103594711A (en) * | 2012-08-15 | 2014-02-19 | 深圳市天骄科技开发有限公司 | Preparation method of lithium iron phosphate material by low-thermal solid-phase microwave method |
| CN106410185A (en) * | 2016-11-11 | 2017-02-15 | 北京理工大学 | Preparation method for lithium ion battery manganese-based cathode materials of egg yolk-egg shell structure |
| CN106663780A (en) * | 2014-07-30 | 2017-05-10 | 三洋电机株式会社 | Positive electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery |
| CN113054168A (en) * | 2019-12-28 | 2021-06-29 | 湖南杉杉能源科技股份有限公司 | Tungsten-molybdenum composite coated ternary cathode material and preparation method thereof |
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| CN101172597A (en) * | 2006-11-01 | 2008-05-07 | 喻维杰 | Industrialization production method of iron lithium phosphate material |
| CN101759172A (en) * | 2009-10-14 | 2010-06-30 | 孙琦 | Microwave sintering method for preparing high-performance iron phosphate lithium |
| CN101800309A (en) * | 2010-04-16 | 2010-08-11 | 中国科学院新疆理化技术研究所 | Microwave synthesis method for multi-element lithium manganate-doped positive electrode material of lithium ion battery |
| CN101901896A (en) * | 2010-06-18 | 2010-12-01 | 鸥瑞智诺能源科技(北京)有限公司 | Safe lithium ion battery anode material and battery thereof |
| CN101920971A (en) * | 2010-06-28 | 2010-12-22 | 宁波大学 | Preparation method of silicate positive electrode material for lithium ion battery |
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2011
- 2011-01-14 CN CN2011100071925A patent/CN102214820A/en active Pending
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| CN101172597A (en) * | 2006-11-01 | 2008-05-07 | 喻维杰 | Industrialization production method of iron lithium phosphate material |
| CN101759172A (en) * | 2009-10-14 | 2010-06-30 | 孙琦 | Microwave sintering method for preparing high-performance iron phosphate lithium |
| CN101800309A (en) * | 2010-04-16 | 2010-08-11 | 中国科学院新疆理化技术研究所 | Microwave synthesis method for multi-element lithium manganate-doped positive electrode material of lithium ion battery |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103594711A (en) * | 2012-08-15 | 2014-02-19 | 深圳市天骄科技开发有限公司 | Preparation method of lithium iron phosphate material by low-thermal solid-phase microwave method |
| CN106663780A (en) * | 2014-07-30 | 2017-05-10 | 三洋电机株式会社 | Positive electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery |
| CN106410185A (en) * | 2016-11-11 | 2017-02-15 | 北京理工大学 | Preparation method for lithium ion battery manganese-based cathode materials of egg yolk-egg shell structure |
| CN106410185B (en) * | 2016-11-11 | 2019-01-25 | 北京理工大学 | A kind of preparation method of the Manganese Based Cathode Materials for Lithium Ion Batteries of yolk-eggshell structure |
| CN113054168A (en) * | 2019-12-28 | 2021-06-29 | 湖南杉杉能源科技股份有限公司 | Tungsten-molybdenum composite coated ternary cathode material and preparation method thereof |
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Application publication date: 20111012 |