CN101527354B - Preparation method of ferrous lithium phosphate cathode composite material - Google Patents
Preparation method of ferrous lithium phosphate cathode composite material Download PDFInfo
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- CN101527354B CN101527354B CN200910043006A CN200910043006A CN101527354B CN 101527354 B CN101527354 B CN 101527354B CN 200910043006 A CN200910043006 A CN 200910043006A CN 200910043006 A CN200910043006 A CN 200910043006A CN 101527354 B CN101527354 B CN 101527354B
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Abstract
The invention relates to a preparation method of a ferrous lithium phosphate cathode composite material. The method comprises the following steps: stocking a ferric iron-source compound, a lithium-source compound, phosphate, doped tantalum compounds and carbon black according to a certain proportion; firstly adding the ferric iron-source compound into an ultrafine ball mill so as to have the graindiameter of 100 nm to 500 nm by ball milling; then, adding other raw materials and using acetone as a dispersant for ball milling and mixing, drying in vacuum and sintering at a low temperature in aninert protective atmosphere oven to deacidize ferric iron; afterwards, adding a certain amount of conductive agent material to obtain ferrous lithium phosphate, ball milling, mixing and drying and sintering at a high temperature in the inert protective atmosphere oven; and finally, shattering, crushing and elutriating to obtain the ferrous lithium phosphate cathode composite material. The invention has the advantages that the materials ensure the tap density and can achieve favorable capacity and magnification performance, and secondary sintering enables the carbon coating to be more even andthe granular magnification to be better.
Description
Technical field
The present invention relates to a kind of preparation method of ferrous lithium phosphate cathode composite material.
Background technology
Lithium rechargeable battery has just been developed rapidly because of its irreplaceable superiority since coming out the nineties in last century.Positive electrode is the chief component of lithium rechargeable battery, and this material mainly contains LiCoO at present
2, LiMn
2O
4Reach the LiFePO that becomes the research focus at present
4Material.LiCoO
2Because its high temperature safe performance is not enough and scarcity metallic cobalt causes being restricted in high-power, jumbo electrokinetic cell application facet; LiMn
2O
4Because its high temperature cyclic performance and security performance are relatively poor, on using, deficiency is also arranged; LiFePO
4Then good cycle, voltage platform are moderate because of having (LiFePO 4), discharge stability, specific capacity are higher, safety and advantage such as pollution-free, have become at present one of the most promising positive electrode.In the production of LiFePO 4, source of iron is to adopt ferrous iron and ferric iron in the majority, and the lithium iron phosphate electrochemical performance of divalence source of iron system is good, but tap density is low, and the iron-holder of divalence source of iron such as ferrous oxalate, ferrous acetate etc. is low, and the cost of raw material is higher; The LiFePO 4 discharge capacity that ferric iron source makes is lower, mainly is that the iron ion quality is bigger, the diffusion difficulty, make the concentration difference of particle surface and inner iron bigger, influence the performance of its capacity, but that benefit is a tap density is higher, and material cost is than about using ferrous salt to be at half.
Summary of the invention
Purpose of the present invention will adopt the ferric iron source compound to produce ferrous lithium phosphate cathode composite material exactly, simultaneously by the improvement to preparation process, to overcome outstanding problems such as its discharge capacity is low.
Technical scheme of the present invention is-a kind of preparation method of ferrous lithium phosphate cathode composite material, it is characterized in that this preparation method comprises following steps successively:
1. with the compound of Li source compound, ferric iron source compound, phosphate and doped metallic elements M in molar ratio Li: Fe: P: M equal (0.9～1.05): 1: (0.95～1.05): the ratio of (0.015～0.8) is prepared burden, and adds the carbon black that can get LiFePO 4 product quality 4-5% in theory again; Earlier with ferric iron source compound ball milling 1～2 hour in ultra-fine ball mill, make its particle diameter be refined into 100～500nm, the compound and the carbon black that add Li source compound, phosphate, doped metallic elements M then are incorporated as the acetone dispersant ball milling 2～5 hours of raw material gross weight 1/1.1 again; With being about to the gained slurry in vacuum drier dry 3～6 hours;
2. with step 1. the bulk goods of gained place atmosphere furnace with argon gas or nitrogen protection, 400～600 ℃ of following sintering 5～12 hours, obtain the graininess LiFePO of grey black
4Material;
3. 2. step is obtained the graininess LiFePO of grey black
4Material drops in the ball mill and carried out ball mill crushing again 1 hour, presses LiFePO then
4With the conductive agent quality of materials than 1: (0.05～0.2) adds the conductive agent material; add the acetone be equal to the raw material gross weight again as dispersant ball milling 2～4 hours; dropped into again in the vacuum drier dry 3～6 hours; at last the bulk goods input of drying is had in the atmosphere furnace of argon gas or nitrogen protection; 780 ℃ of following sintering 12 hours, obtain ferrous lithium phosphate cathode composite material through fragmentation, pulverizing, classification again.
In concrete the enforcement, described Li source compound is one or more the mixture in lithium carbonate, lithium hydroxide, the lithium dihydrogen phosphate; Described ferric iron source compound is one or more the mixture in di-iron trioxide, the ferric phosphate; Described phosphate compounds is one or both the mixture in ferric phosphate, ammonium di-hydrogen phosphate, the lithium dihydrogen phosphate, and the compound of described doped metallic elements M then is one or more the mixture in the compound of cobalt, manganese, titanium, magnesium, niobium, aluminium. described conductive agent material is one or more the mixture in graphite, carbon black, starch, glucose, the sucrose.
Advantage of the present invention is: adopt ferric iron source, the tap density of product can be guaranteed; Before once sintered, adopt ultra-fine ball-milling treatment, make refinement particle can with the even mixed distribution of carbon, can reach preferable capacity and high rate performance, can guarantee to greatest extent that ferric iron is a ferrous iron by carbon reduction simultaneously, the raising capacity guarantees chemical property; Double sintering is handled and is made carbon coat more homogeneous, and the particle multiplying power is also better.
Embodiment
Example one: get the 20kg di-iron trioxide and added in the ultra-fine ball mill ball milling 2 hours; make its particle diameter reach 100～500nm; add the 9.25kg lithium carbonate then; 28.75kg ammonium di-hydrogen phosphate; 0.4kg titanium dioxide; 1.6kg carbon black; add 50kg acetone again and make the dispersant ball milling after 3 hours; in vacuum drier, made dry materials become red coccoid in dry 3～6 hours; the atmosphere furnace that again this coccoid material input is had a nitrogen protection was in 550 ℃ of following heat preservation sinterings 10 hours; obtain the grey black LiFePO 4; and then put in the ball mill ball mill crushing 1 hour; added 4kg glucose and 40kg acetone dispersant ball milling again 2 hours; thereafter drying made into coccoid in 3～6 hours in vacuum drier; drop into again in the atmosphere furnace of nitrogen protection 780 ℃ of following sintering 12 hours, promptly obtain ferrous lithium phosphate cathode composite material.Carry out Mechanical Crushing, mechanical crushing, graded operation at last and obtain formal product.Product is carried out showing that it meets the quadrature olivine structural of pure phase after XRD detects; And physical index detects and shows that the product tap density is 1.5g/cm
3, granularity D50 is 3.9 μ m, specific area is 13.6m
2/ g.
This product as positive active material, is made positive plate according to common process, is barrier film with the microporous polypropylene membrane, and electrolyte is the LiPF of 1mol/L
6: ethylene carbonate+dimethyl carbonate=1: 1 (volume ratio), with the lithium sheet is negative pole, in the glove box of nitrogen protection, make 2025 type button cells, (condition: charging/discharging voltage is 2.5～4.2V to carry out the performance test of battery charging and discharging with the cell tester of the blue electricity in Wuhan again, charge-discharge magnification is respectively 0.2C, 0.5C), 0.2C the battery first discharge specific capacity is 144mAh/g, the average discharging efficiency of first three time is that 96%, 50 circulation volume remains 96.6%; 0.5C the first discharge specific capacity of battery is 133mAh/g, the average discharging efficiency of first three time is that 95%, 50 circulation volume remains 95.8%.
Example two: get the 20kg di-iron trioxide and went in the ultra-fine ball mill ball milling 2 hours; make its particle diameter reach 100～500nm; add the 26kg lithium dihydrogen phosphate then; 0.4kg titanium dioxide and 1.6kg carbon black; added 50kg acetone dispersant ball milling again 3 hours; went in the vacuum drier dry 3～6 hours; again the coccoid dried material input of redness is had in the atmosphere furnace of nitrogen protection 550 ℃ of following heat preservation sinterings 10 hours; obtain the grey black LiFePO 4; LiFePO 4 was sent in the ball mill ball mill crushing 1 hour; added 4kg glucose and 40kg acetone ball milling again 2 hours; drop into afterwards in the vacuum drier and to make into coccoid in dry 3～6 hours; drop into again in the atmosphere furnace of nitrogen protection 780 ℃ of sintering 12 hours; carry out Mechanical Crushing at last; mechanical crushing; graded operation promptly gets ferrous lithium phosphate cathode composite material product finally.
After testing, the tap density of this material is 1.4g/cm
3, granularity D50 is 4.1 μ m.After this material made 2025 type button cells, detect show 0.5C first discharge capacity be 132mAh/g, 50 times the circulation volume conservation rate is 96.2%.
Example three: get the 37.8kg ferric phosphate and went in the ultra-fine ball mill ball milling 2 hours, add 9.25kg lithium carbonate, 0.4kg titanium dioxide and 1.6kg carbon black then, added 50kg acetone ball milling again 3 hours, with gained material material in vacuum drier dry 3～6 hours; With in the atmosphere furnace that is about to the coccoid dried material input of gained white and has nitrogen protection 550 ℃ of following heat preservation sinterings 10 hours, can get grey black LiFePO 4 (LiFePO
4) material; with grey black ferrousphosphate lithium material ball mill crushing 1 hour in ball mill; added 4kg glucose and 40kg acetone ball milling again 2 hours; drying made into coccoid in 3～6 hours in vacuum drier afterwards; drop into again in the atmosphere furnace of nitrogen protection 780 ℃ of following sintering 12 hours; carry out Mechanical Crushing, mechanical crushing, graded operation at last, obtain final ferrous lithium phosphate cathode composite material product.
After testing, the tap density of this material is 1.43g/cm
3, granularity D50 is 4.5 μ m.Detect after its method by example 1 made 2025 type button cells, 0.5C discharge capacity first is 129mAh/g, and 50 times the circulation volume conservation rate is 95.5%.
Claims (3)
1. the preparation method of a ferrous lithium phosphate cathode composite material is characterized in that, this preparation method comprises following steps successively:
1. with the compound of Li source compound, ferric iron source compound, phosphate and doped metallic elements M in molar ratio Li: Fe: P: M equal (0.9～1.05): 1: (0.95～1.05): the ratio of (0.015～0.8) is prepared burden, and adds the carbon black that can get LiFePO 4 product quality 4-5% in theory again; Earlier with ferric iron source compound ball milling 1～2 hour in ultra-fine ball mill, make its particle diameter be refined into 100～500nm, the compound and the carbon black that add Li source compound, phosphate, doped metallic elements M then are incorporated as the acetone dispersant ball milling 2～5 hours of raw material gross weight 1/1.1 again; With being about to the gained slurry in vacuum drier dry 3～6 hours;
2. with step 1. the bulk goods of gained place atmosphere furnace with argon gas or nitrogen protection, 400～600 ℃ of following sintering 5～12 hours, obtain the graininess LiFePO of grey black
4Material;
3. 2. step is obtained the graininess LiFePO of grey black
4Material drops in the ball mill and carried out ball mill crushing again 1 hour, presses LiFePO then
4With the conductive agent quality of materials than 1: (0.05～0.2) adds the conductive agent material; add the acetone be equal to the raw material gross weight again as dispersant ball milling 2～4 hours; dropped into again in the vacuum drier dry 3～6 hours; at last the bulk goods input of drying is had in the atmosphere furnace of argon gas or nitrogen protection; 780 ℃ of following sintering 12 hours, obtain ferrous lithium phosphate cathode composite material through fragmentation, pulverizing, classification again.
2. the preparation method of a kind of ferrous lithium phosphate cathode composite material according to claim 1 is characterized in that, described Li source compound is one or more the mixture in lithium carbonate, lithium hydroxide, the lithium dihydrogen phosphate; Described ferric iron source compound is one or more the mixture in di-iron trioxide, the ferric phosphate; Described phosphate compounds is one or both the mixture in ferric phosphate, ammonium di-hydrogen phosphate, the lithium dihydrogen phosphate, and the compound of described doped metallic elements M then is one or more the mixture in the compound of cobalt, manganese, titanium, magnesium, niobium, aluminium.
3. the preparation method of a kind of ferrous lithium phosphate cathode composite material according to claim 1 is characterized in that, described conductive agent material is one or more the mixture in graphite, carbon black, starch, glucose, the sucrose.
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|---|---|---|---|---|
| CN101920952B (en) * | 2010-08-24 | 2011-11-02 | 天津伊博瑞尔能源科技发展有限公司 | Technique and device for producing iron phosphate lithium positive pole material through one-step process |
| CN102881902B (en) * | 2012-10-22 | 2015-09-16 | 山东海特电子新材料有限公司 | A kind of method of suitability for industrialized production lithium iron phosphate positive material |
| CN104409731A (en) * | 2014-12-11 | 2015-03-11 | 中信大锰矿业有限责任公司大新锰矿分公司 | Doped lithium iron phosphate and preparation method |
| CN105870420B (en) * | 2016-05-27 | 2018-06-19 | 天津巴莫科技股份有限公司 | A kind of lithium-ion-power cell manganese-lithium phosphate anode material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1677718A (en) * | 2004-03-30 | 2005-10-05 | 中国科学院物理研究所 | A kind of preparation method of the phosphate cathode material of lithium ion battery |
| EP1689011A1 (en) * | 2003-10-27 | 2006-08-09 | MITSUI ENGINEERING & SHIPBUILDING CO., LTD | Positive electrode material for secondary battery, method for producing positive electrode material for secondary battery, and secondary battery |
| CN101154728A (en) * | 2007-09-07 | 2008-04-02 | 清华大学 | Method for producing ultra-fine LiFePO4/C of lithium ion battery anode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1689011A1 (en) * | 2003-10-27 | 2006-08-09 | MITSUI ENGINEERING & SHIPBUILDING CO., LTD | Positive electrode material for secondary battery, method for producing positive electrode material for secondary battery, and secondary battery |
| CN1677718A (en) * | 2004-03-30 | 2005-10-05 | 中国科学院物理研究所 | A kind of preparation method of the phosphate cathode material of lithium ion battery |
| CN101154728A (en) * | 2007-09-07 | 2008-04-02 | 清华大学 | Method for producing ultra-fine LiFePO4/C of lithium ion battery anode material |
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