CN103441273A - Preparation method for energy-storage type lithium iron phosphate composite material - Google Patents
Preparation method for energy-storage type lithium iron phosphate composite material Download PDFInfo
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- CN103441273A CN103441273A CN2013103860058A CN201310386005A CN103441273A CN 103441273 A CN103441273 A CN 103441273A CN 2013103860058 A CN2013103860058 A CN 2013103860058A CN 201310386005 A CN201310386005 A CN 201310386005A CN 103441273 A CN103441273 A CN 103441273A
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method for an energy-storage type lithium iron phosphate composite material. The preparation method comprises the following steps of: uniformly mixing a lithium source, a ferrous source and a phosphoric acid source, then sintering in an inert atmosphere to obtain a phosphate sintered material; performing a crushing-grading treatment on the phosphate sintered material to obtain a phosphate material; and then spheroidizing and coating the phosphate material and a carbon source by a mechanical fusion machine to obtain the carbon-coated type lithium iron phosphate composite material. Via the mode aforementioned, the preparation method for the energy-storage type lithium iron phosphate composite material disclosed by the invention adopts a dry-method carbon-coating technology, thus working procedures are simplified, energy consumption and working hours can be remarkably reduced, the needs of low-cost and high-quality lithium manganese phosphate are met, the tap density of lithium iron phosphate is effectively increased, and the rate characteristic of lithium iron phosphate is improved; and the preparation method is moderate in reaction conditions, obviously increased in yield, suitable for industrialized production, and capable of enhancing the competitiveness of phosphate cells in the aspect of energy-storage type cells.
Description
Technical field
The present invention relates to the battery material preparation field, particularly relate to a kind of preparation method of accumulation energy type composite ferric lithium phosphate material.
Background technology
LiFePO 4 material is because its excellent security performance and outstanding cycle performance become the composite material of first-selected lithium dynamical battery, and LiFePO 4 material also is widely used in the ups power system of mobile phone, notebook computer, digital camera and other a large amount of emerging IT product in addition.But there is the defect that electronic conductivity is low in LiFePO 4 material itself, thereby restricted its application in certain fields.
The method of the electronic conductivity of the raising iron lithium phosphate material of at present verified maturation coats for carry out surface by organic carbon or DIC, conductivity can be promoted to 7 orders of magnitude, but technique has defect in actual production now, have, the introducing of organic carbon can cause limiting growing up of lithium iron phosphate particles in sintering process, be conducive to although it is so the improvement of high rate performance, but decrease tap density and the energy density of material.Because the discharge-rate at energy storage field material is very little, generally be no more than 0.2C, so the lifting of energy density has significant impact to the cost that reduces energy-storage module.Simultaneously traditionally add the particle manufacture inequality that the carbon sintering process can make material, the yield of release mesh is less than 80%.
Summary of the invention
The technical problem that the present invention mainly solves is to provide a kind of preparation method of accumulation energy type composite ferric lithium phosphate material, and the method operation is simple, is applicable to suitability for industrialized production.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: the preparation method that a kind of accumulation energy type composite ferric lithium phosphate material is provided, comprise that step is: by the lithium source, after ferrous source and source of phosphoric acid mix in inert atmosphere sintering obtain the phosphate sintering feed, described phosphate sintering feed after processing, crushing and classification is obtained to phosphate material, again phosphate material and carbon source are carried out to nodularization and coat by machinery fusion machine obtaining the composite ferric lithium phosphate material that carbon coats, wherein said lithium source, lithium ion in described ferrous source and described source of phosphoric acid, the mol ratio of ferrous ion and phosphate radical is 1:(0.98 ~ 1.02): (0.97 ~ 1.03).
In a preferred embodiment of the present invention, described lithium source is lithium carbonate, and described ferrous source is ferrous oxalate, and described source of phosphoric acid is ammonium dihydrogen phosphate.
In a preferred embodiment of the present invention, described lithium source is battery-level lithium carbonate, the purity of described lithium carbonate is greater than 99.5%, described ferrous source is battery level iron oxalate, the purity of described ferrous oxalate is greater than 98%, described source of phosphoric acid is for analyzing the pure phosphoric acid ammonium dihydrogen, and the purity of described ammonium dihydrogen phosphate is greater than 99.5%.
In a preferred embodiment of the present invention, described sintering process is 500 ~ 750 ℃ of lower sintering 6 ~ 12 hours.
In a preferred embodiment of the present invention, the equipment adopted in described crushing and classification processing procedure is that air-flowing type pulverizing grading machine or mechanical type are pulverized grader.
In a preferred embodiment of the present invention, the granularity of described phosphate material is D
50between 0.5 ~ 3.0um, D
99be less than or equal to 9um.
In a preferred embodiment of the present invention, the mixture that described carbon source is conductive black, acetylene black or conductive black and acetylene black, the covering amount of described carbon source is 3 ~ 8% of described phosphate material and described carbon source gross mass.
The invention has the beneficial effects as follows: the preparation method of accumulation energy type composite ferric lithium phosphate material of the present invention, adopt dry method bag carbon technique, simplify operation, can significantly reduce energy consumption and shorten man-hour, met the demand of low-cost high-quality LiFePO4, effectively improved the tap density of LiFePO4, improved the multiplying power property of LiFePO4, the reaction condition gentleness, yield obviously improves, be applicable to suitability for industrialized production, strengthened the competitiveness of phosphate battery aspect the accumulation energy type battery.
The accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, in below describing embodiment, the accompanying drawing of required use is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings, wherein:
Fig. 1 is the crystallogram of the composite ferric lithium phosphate material that obtains of the embodiment of the present invention one, adopts CuK α target emanation, λ=0.15416 nm;
Fig. 2 is Electronic Speculum (SEM) picture of the composite ferric lithium phosphate material that obtains of the embodiment of the present invention one;
Fig. 3 is the high rate performance discharge curve of the composite ferric lithium phosphate material that obtains of the embodiment of the present invention one, employing be 2032 button cells, and do negative pole with the lithium sheet.
Embodiment
Below will the technical scheme in the embodiment of the present invention be clearly and completely described, obviously, described embodiment is only a part of embodiment of the present invention, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making all other embodiment that obtain under the creative work prerequisite, belong to the scope of protection of the invention.
Embodiment mono-:
(1) under normal temperature, get the battery-level lithium carbonate of 20.93kg, the battery level iron oxalate of 101.48kg and the chemical pure ammonium dihydrogen phosphate of 64.54kg, above-mentioned three kinds of materials are mixed 2 hours in three-dimensional material mixer;
(2) again mixtures of materials is placed in to the nitrogen protection atmosphere stove and carries out sintering, pure ferric phosphate lithium material after sintering carries out the crushing and classification processing with jet mill, pressure during pulverizing is 10MPa, the particle size distribution of the LiFePO4 material of discharging will meet D50 between 0.5 ~ 1.0um, and D99 is no more than 5um;
(3) conductive black that the material after crushing and classification is merged to machine and 3% by machinery merges to coat to process and obtains composite ferric lithium phosphate material, and its physical and chemical performance characterizes sees Fig. 1, Fig. 2 and Fig. 3.XRD shows without dephasign, the material particle size narrowly distributing that this legal system is standby, and chemical property is good, and specific discharge capacity is up to 150mAh/g, voltage range 2.65V ~ 4.2V, discharge-rate 0.1C.
Embodiment bis-:
(1) under normal temperature, get the battery-level lithium carbonate of 20.93kg, the electron level ferrous oxalate of 101.48kg and the chemical pure ammonium dihydrogen phosphate of 64.54kg, above-mentioned three kinds of materials are mixed 2 hours in three-dimensional material mixer;
(2) again mixtures of materials is placed in to the nitrogen protection atmosphere stove and carries out sintering, pure ferric phosphate lithium material after sintering carries out the crushing and classification processing with mechanical crusher, the particle size distribution of the LiFePO4 material of discharging will meet D50 between 2.0 ~ 3.0um, and D99 is no more than 9um;
(3) conductive black of the material after crushing and classification and 3% is merged to the coating processing by machinery fusion machine and obtain composite ferric lithium phosphate material.
Embodiment tri-:
(1) under normal temperature, get the battery-level lithium carbonate of 20.90kg, the electron level ferrous oxalate of 100.38kg and the chemical pure ammonium dihydrogen phosphate of 64.54kg, above-mentioned three kinds of materials are mixed 2 hours in three-dimensional material mixer;
(2) again mixtures of materials is placed in to the nitrogen protection atmosphere stove and carries out sintering, pure ferric phosphate lithium material after sintering carries out the crushing and classification processing with mechanical crusher, the particle size distribution of the LiFePO4 material of discharging will meet D50 between 2.0 ~ 3.0um, and D99 is no more than 9um;
(3) conductive black of the material after crushing and classification and 3%, 3% acetylene black are merged coat to process and obtain composite ferric lithium phosphate material.
The preparation method's of accumulation energy type composite ferric lithium phosphate material of the present invention beneficial effect is:
One, coat fine and close carbon-coating by the inorganic bag carbon of dry method technique on the LiFePO4 surface, avoided on the one hand organic carbon inevitable reduction reaction of crossing in pyroprocess, in high-temperature reaction process, the LiFePO4 nucleus can uncontrolledly increase on the other hand, reduced the existence of fine particle, this is also to affect processing characteristics to cause pole piece to cut the key factor of dry linting in the battery core preparation process, research shows that larger particle has remarkable effect to self discharge and the high temperature that improves battery, need good processability in the energy-storage battery field especially, the composite material that high-temperature behavior is good.
Two, the size of LiFePO4 primary particle that adopted carbon-free sintering process to improve, effectively raise like this tap density of material, further improved drawing abillity and the battery energy density under little multiplying power discharging, experimental results show that the surface density of the film-making of material in battery manufacturing process can reach 420g/m
2, this has reached the level of current nickle cobalt lithium manganate basically.
Three, adopt air-flow or mechanical type to pulverize classification our original lithium iron phosphate particles is carried out to finely regulating, allow it reach the particle property that we require, consistency significantly strengthens, and product yield obviously increases, and the yield of release mesh can be promoted to 95%;
Four, mechanical fusion method, by spheroidizing of particles, has improved the mobility of material, and the slurry that closes that is conducive to the battery core making operates, and the introducing of DIC simultaneously coats the multiplying power property of having improved LiFePO4.
Five, with traditional solid sintering technology, compare, method of the present invention does not need solvent to carry out batch mixing, stopped the dry run in the traditional handicraft process, adopt physics nodularization and coating technology to improve the uncontrollable problem of phosphate material pattern, there is processing characteristics good, the significant advantage that energy density is high.
The foregoing is only embodiments of the invention; not thereby limit the scope of the claims of the present invention; every equivalent structure or conversion of equivalent flow process that utilizes description of the present invention to do; or directly or indirectly be used in other relevant technical field, all in like manner be included in scope of patent protection of the present invention.
Claims (7)
1. the preparation method of an accumulation energy type composite ferric lithium phosphate material, it is characterized in that, comprise that step is: by the lithium source, after ferrous source and source of phosphoric acid mix in inert atmosphere sintering obtain the phosphate sintering feed, described phosphate sintering feed after processing, crushing and classification is obtained to phosphate material, again phosphate material and carbon source are carried out to nodularization and coat by machinery fusion machine obtaining the composite ferric lithium phosphate material that carbon coats, wherein said lithium source, lithium ion in described ferrous source and described source of phosphoric acid, the mol ratio of ferrous ion and phosphate radical is 1:(0.98 ~ 1.02): (0.97 ~ 1.03).
2. preparation method according to claim 1, is characterized in that, described lithium source is lithium carbonate, and described ferrous source is ferrous oxalate, and described source of phosphoric acid is ammonium dihydrogen phosphate.
3. preparation method according to claim 2, it is characterized in that, described lithium source is battery-level lithium carbonate, the purity of described lithium carbonate is greater than 99.5%, described ferrous source is battery level iron oxalate, the purity of described ferrous oxalate is greater than 98%, and described source of phosphoric acid is for analyzing the pure phosphoric acid ammonium dihydrogen, and the purity of described ammonium dihydrogen phosphate is greater than 99.5%.
4. preparation method according to claim 1, is characterized in that, described sintering process is 500 ~ 750 ℃ of lower sintering 6 ~ 12 hours.
5. preparation method according to claim 1, is characterized in that, the equipment adopted in described crushing and classification processing procedure is that air-flowing type pulverizing grading machine or mechanical type are pulverized grader.
6. preparation method according to claim 1, is characterized in that, the granularity of described phosphate material is D
50between 0.5 ~ 3.0um, D
99be less than or equal to 9um.
7. preparation method according to claim 1, is characterized in that, the mixture that described carbon source is conductive black, acetylene black or conductive black and acetylene black, and the covering amount of described carbon source is 3 ~ 8% of described phosphate material and described carbon source gross mass.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108054378A (en) * | 2017-12-29 | 2018-05-18 | 中国科学院物理研究所 | Lithium battery composite positive pole with nucleocapsid and preparation method thereof |
| CN109390579A (en) * | 2018-06-29 | 2019-02-26 | 福建金山锂科新材料有限公司 | A kind of preparation method of the nickelic tertiary cathode material of dry and wet carbon coating |
| CN112259721A (en) * | 2020-10-28 | 2021-01-22 | 湖北融通高科先进材料有限公司 | Lithium iron phosphate-lithium-rich oxide compound and preparation method thereof |
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| CN101830453A (en) * | 2010-05-27 | 2010-09-15 | 谢朝华 | Secondary sintering synthesis method for lithium iron phosphate |
| CN102856546A (en) * | 2012-09-20 | 2013-01-02 | 江苏福瑞士新能源有限公司 | Method for preparing lithium iron phosphate material by raw material solid phase dry grinding |
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- 2013-08-30 CN CN2013103860058A patent/CN103441273A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1180811A2 (en) * | 2000-08-18 | 2002-02-20 | Sony Corporation | Non-aqueous electrolyte secondary cell |
| CN1340869A (en) * | 2000-08-30 | 2002-03-20 | 索尼株式会社 | Cathode active material and its preparation method, nonaqueous dielectric cell and its preparation method |
| CN101830453A (en) * | 2010-05-27 | 2010-09-15 | 谢朝华 | Secondary sintering synthesis method for lithium iron phosphate |
| CN102856546A (en) * | 2012-09-20 | 2013-01-02 | 江苏福瑞士新能源有限公司 | Method for preparing lithium iron phosphate material by raw material solid phase dry grinding |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108054378A (en) * | 2017-12-29 | 2018-05-18 | 中国科学院物理研究所 | Lithium battery composite positive pole with nucleocapsid and preparation method thereof |
| CN109390579A (en) * | 2018-06-29 | 2019-02-26 | 福建金山锂科新材料有限公司 | A kind of preparation method of the nickelic tertiary cathode material of dry and wet carbon coating |
| CN112259721A (en) * | 2020-10-28 | 2021-01-22 | 湖北融通高科先进材料有限公司 | Lithium iron phosphate-lithium-rich oxide compound and preparation method thereof |
| CN112259721B (en) * | 2020-10-28 | 2023-01-17 | 湖北融通高科先进材料集团股份有限公司 | Lithium iron phosphate-lithium-rich oxide compound and preparation method thereof |
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