CN102074689B - Method for preparing lithium iron phosphate composite material - Google Patents
Method for preparing lithium iron phosphate composite material Download PDFInfo
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- CN102074689B CN102074689B CN201010602891XA CN201010602891A CN102074689B CN 102074689 B CN102074689 B CN 102074689B CN 201010602891X A CN201010602891X A CN 201010602891XA CN 201010602891 A CN201010602891 A CN 201010602891A CN 102074689 B CN102074689 B CN 102074689B
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Abstract
The invention discloses a method for preparing a lithium iron phosphate composite material. The method comprises the following steps of: 1) preparing a titanium-doped precursor, namely adding a lithium source, an iron source, a titanium source and a phosphorus source according to the molar ratio of (1-1.05):(0.97-0.995):(0.005-0.03):1 into a ball mill together with a carbon source, ball-milling for 6 to 12 hours, performing spray drying and sieving; 2) preparing titanium-doped lithium iron phosphate, namely calcining dried materials under the protection of inert gas at the temperature of between 350 and 500 DEG C for 3 to 5 hours, crushing, and calcining at the temperature of between 600 and 800 DEG C for 8 to 16 hours; and 3) coating titanium dioxide, namely mixing the titanium-doped lithium iron phosphate prepared in the step 2) and the titanium source, drying, and calcining in the inert gas at the temperature of between 400 and 800 DEG C for 4 to 8 hours. The lithium iron phosphate composite material prepared by the method has higher compactness, high electrochemical performance and high machining performance; and the method has a relatively stable process and is easy to industrialize.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries, particularly relate to a kind of preparation method of composite ferric lithium phosphate material.
Background technology
LiFePO4 (LiFePO
4), environmental friendliness cheap because of its cost of material, specific capacity be high, characteristics such as cycle performance and security performance excellence particularly, make it in the required large-sized power field of power supplies of various movable power sources field, particularly electric motor car great market prospects be arranged, be considered to the anode material for lithium-ion batteries of new generation of tool development and application potentiality.But LiFePO
4Exist conductivity to hang down the shortcoming that spreads rate variance with ion, cause high-rate charge-discharge capability poor low with actual specific capacity, this has greatly limited its extensive use in practical field.
People's research attentiveness mainly concentrates on this field of LiFePO4 conductivity that solves at present.Improve LiFePO
4The main method of conductivity is that carbon coats and metal ion mixing.And existing carbon method for coating can significantly reduce the tap density of material, causes its volume energy density lower, is difficult to practical application; Although existing metal ion mixing method has increased substantially the conductivity of material, also have certain gap apart from expectation target, remain to be further improved.
Summary of the invention
The purpose of this invention is to provide that a kind of good conductivity, volume energy density are high, chemical property and the processing characteristics preparation method of composite ferric lithium phosphate material preferably.
The objective of the invention is to be achieved through the following technical solutions:
A kind of preparation method of composite ferric lithium phosphate material is characterized in that may further comprise the steps:
1) the titanium precursor body is mixed in preparation: with lithium source, source of iron, titanium source and phosphorus source according to mol ratio 1～1.05: with carbon source join in ball mill at 0.97～0.995: 0.005～0.03: 1, the consumption of carbon source makes its mass percent in finished product less than 2%, add quantitative deionized water and zirconium ball and do abrasive media, ball milling 6～12 hours, after making the raw material porphyrize and mixing, carry out spray drying, sieve;
2) the titanium LiFePO4 is mixed in preparation: dried material under inert gas shielding, 350～500 ℃ of calcinings 3～5 hours, was calcined 8～16 hours at 600 ℃～800 ℃ after pulverizing;
3) cladding titanium dioxide: with step 2) preparation mix titanium LiFePO4 and titanium source behind combination drying, under inert gas, calcined 4～8 hours in 400 ℃～800 ℃.
Described source of iron is ferrous oxalate, iron oxide or ferric phosphate;
Described lithium source is lithium carbonate, lithium hydroxide or lithium dihydrogen phosphate;
Described phosphorus source is ammonium dihydrogen phosphate, ferric phosphate or lithium dihydrogen phosphate;
Described carbon source is glucose sugar, sucrose, polyethylene glycol, citric acid or superconduction carbon black;
Step 1) described titanium source is titanium dioxide, lithium titanate, titanium sulfate or butyl titanate;
Step 3) described titanium source is titanium dioxide or butyl titanate;
Step 1) it is 1: 1～2 (quality) that the quantitative deionized water of the adding described in satisfies solid-to-liquid ratio;
Step 1) it is 2～4: 1 (quality) that the quantitative zirconium ball of the adding described in satisfies ratio of grinding media to material;
Step 1) it is 1: 1～2 (quality) that the quantitative deionized water of the adding described in satisfies solid-to-liquid ratio;
Step 1) it is 2～4: 1 (quality) that the quantitative zirconium ball of the adding described in satisfies ratio of grinding media to material;
Step 1) drying described in is spray drying;
Step 3) solid-phase ball milling that is mixed into described in mixes, and ratio of grinding media to material is 1～2: 1, and Ball-milling Time is 0.5～2 hour;
Step 3) described mixing can also be that the wet method super-fine ball milling mixes, and solid content is 50%, and Ball-milling Time is 1～2 hour;
Step 3) described its covering amount of cladding titanium dioxide is described 0.8%～2% of the titanium LiFePO4 quality of mixing.
The invention has the advantages that: in building-up process, except passing through Doped with Titanium ion (Ti
4+), replace iron position a small amount of in the LiFePO4, outside the conductivity that improves LiFePO 4 material, also adopting outside carbon coated again, cladding titanium dioxide improves LiFePO
4The conductivity of material further improves its high rate charge-discharge performance.Owing to having reduced the consumption (below 2%) of carbon coated, so effectively improved the tap density of material, having increased the volumetric specific energy of material.Doped with Titanium ion (the Ti that adopts preparation method of the present invention to produce
4+) LiFePO of cladding titanium dioxide simultaneously
4Composite material has higher tap density, and good chemical property and processing characteristics.In addition, the preparation method of the low-carbon (LC) composite ferric lithium phosphate material of titanium doped and cladding titanium dioxide of the present invention, process stabilizing, step are relatively simple, easily realize industrialization.
Description of drawings
Fig. 1 is composite ferric lithium phosphate material preparation method's of the present invention flow chart;
Fig. 2 is the XRD figure of the prepared according to the methods of the invention low-carbon (LC) composite ferric lithium phosphate material of mixing titanium and cladding titanium dioxide;
Fig. 3 is the SEM figure of the prepared according to the methods of the invention low-carbon (LC) composite ferric lithium phosphate material of mixing titanium and cladding titanium dioxide.
Embodiment
Referring to Fig. 1, the preparation method of composite ferric lithium phosphate material of the present invention may further comprise the steps:
1) the titanium precursor body is mixed in preparation: with lithium source, source of iron, titanium source and phosphorus source according to mol ratio 1～1.05: with carbon source join in ball mill at 0.97～0.995: 0.005～0.03: 1, the consumption of carbon source makes its mass percent in finished product less than 2%, add quantitative deionized water and zirconium ball and do abrasive media, ball milling 6～12 hours, after making the raw material porphyrize and mixing, carry out spray drying, sieve;
2) the titanium LiFePO4 is mixed in preparation: dried material under inert gas shielding, 350～500 ℃ of calcinings 3～5 hours, was calcined 8～16 hours at 600 ℃～800 ℃ after pulverizing;
3) cladding titanium dioxide: with step 2) preparation mix titanium LiFePO4 and titanium source behind combination drying, under inert gas, calcined 4～8 hours in 400 ℃～800 ℃.
Described source of iron is ferrous oxalate, iron oxide or ferric phosphate;
Described lithium source is lithium carbonate, lithium hydroxide or lithium dihydrogen phosphate;
Described phosphorus source is ammonium dihydrogen phosphate, ferric phosphate or lithium dihydrogen phosphate;
Described carbon source is glucose sugar, sucrose, polyethylene glycol, citric acid or superconduction carbon black;
Step 1) described titanium source is titanium dioxide, lithium titanate, titanium sulfate or butyl titanate;
Step 3) described titanium source is titanium dioxide or butyl titanate.
Below in conjunction with specific embodiment preparation method of the present invention is elaborated:
Embodiment 1
In ball mill, add 5kg zirconium ball and 2.5L deionized water, add while stirring 2.4875molFe
2O
3, 2.575mol Li
2CO
3, 5mol NH
4H
2PO
4, 0.025mol Ti (SO
4)
2(being dissolved in water), and 81g glucose, ball milling 6 hours after making the raw material porphyrize and mixing, carries out spray drying, crosses 100 mesh sieves; To mix the titanium precursor body under argon shield after the spray drying, in 350 ℃ of calcinings 5 hours, after discharging is pulverized at 750 ℃ of calcining 16h; That gets generation mixes titanium LiFePO4 600g, adds titanium dioxide 12.25g, and 650g zirconium ball, solid-phase ball milling be after 2 hours, and under inert gas 400 ℃, calcining 8h.The tap density of products obtained therefrom is 1.31g/ml, and phosphorus content is 1.27%; The battery of making, 1C discharge capacity are 125mAh/g.
In ball mill, add 5kg zirconium ball and 2.4L deionized water, add while stirring 4.925mol ferrous oxalate, 5mol LiH
2PO
4, 0.015mol Li
4Ti
5O
12, the 200g polyethylene glycol, ball milling 12 hours after making the raw material porphyrize and mixing, carries out spray drying, crosses 100 mesh sieves; To mix the titanium precursor body under argon shield after the spray drying, in 400 ℃ of calcinings 4 hours, after discharging is pulverized at 600 ℃ of calcining 12h; That gets generation mixes titanium LiFePO4 600g, and adding 230mL concentration is the ethanolic solution of 0.5mol/L butyl titanate, adds 400g water again, ultra-fine ball milling 2h, spray drying then, under inert gas conditions 700 ℃ at last, calcining 6h.The tap density of products obtained therefrom is 1.18g/ml, and phosphorus content is 1.73%; The battery of making, 1C discharge capacity are 132mAh/g.
Embodiment 3
In ball mill, add 2kg zirconium ball and 1L deionized water, add while stirring 4.85mol ferric phosphate, 5.25mol LiOHH
2O, 0.15mol NH
4H
2PO
4, 300mL concentration is 0.5mol/L butyl titanate ethanolic solution and 27g superconduction carbon black, ball milling 8 hours after making the raw material porphyrize and mixing, carries out spray drying, crosses 100 mesh sieves; To mix the titanium precursor body under argon shield after the spray drying, in 500 ℃ of calcinings 3 hours, after discharging is pulverized at 800 ℃ of calcining 8h; That gets preparation mixes titanium LiFePO4 600g, adds titanium dioxide 5g, and 1.2kg zirconium ball, solid-phase ball milling be after 0.5 hour, and under inert gas 800 ℃, calcining 4h.The tap density of products obtained therefrom is 1.24g/ml, and phosphorus content is 1.46%; The battery of making, 1C discharge capacity are 129mAh/g.
Can find out that from the XRD figure (Fig. 2) of synthetic sample a small amount of coated by titanium dioxide does not cause the marked change that material forms, not find dephasign, still be the LiFePO4 peak of pure phase.
From the SEM figure (Fig. 3) of synthetic sample, can find out synthetic sample, be the aggregation of fine particle, the distribution homogeneous, the raising high rate performance that so namely is conducive to material can improve drawing abillity again.
Claims (6)
1. the preparation method of a composite ferric lithium phosphate material is characterized in that may further comprise the steps:
1) the titanium precursor body is mixed in preparation: with lithium source, source of iron, titanium source and phosphorus source according to mol ratio 1～1.05: with carbon source join in ball mill at 0.97～0.995: 0.005～0.03: 1, the consumption of carbon source makes the mass percent of carbon in the finished product less than 2%, add quantitative deionized water and zirconium ball and do abrasive media, ball milling 6～12 hours, after making the raw material porphyrize and mixing, carry out spray drying, sieve, it is 1: 1～2 that the quantitative deionized water of wherein said adding satisfies the solid-liquid mass ratio;
2) the titanium LiFePO4 is mixed in preparation: dried material under inert gas shielding, 350～500 ℃ of calcinings 3～5 hours, was calcined 8～16 hours at 600 ℃～800 ℃ after pulverizing;
3) cladding titanium dioxide: with step 2) preparation mix titanium LiFePO4 and titanium source after mixing drying, under inert gas, calcined 4～8 hours in 400 ℃～800 ℃.
2. preparation method according to claim 1 is characterized in that: step 1) described titanium source is titanium dioxide, lithium titanate, titanium sulfate or butyl titanate; Step 3) described titanium source is titanium dioxide or butyl titanate.
3. preparation method according to claim 1 is characterized in that: step 1) described in the quantitative zirconium ball of adding to satisfy ratio of grinding media to material be 2～4: 1 (quality).
4. preparation method according to claim 1 is characterized in that: step 3) described in the solid-phase ball milling that is mixed into mix, ratio of grinding media to material is 1～2: 1, Ball-milling Time is 0.5～2 hour.
5. preparation method according to claim 1 is characterized in that: step 3) the described wet method super-fine ball milling that is mixed into mixes, and solid content is 50%, and Ball-milling Time is 1～2 hour.
6. preparation method according to claim 1 is characterized in that: step 3) in the covering amount of titanium dioxide be described 0.8%～2% of the titanium LiFePO4 quality of mixing.
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Families Citing this family (21)
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| CN102509801A (en) * | 2011-11-15 | 2012-06-20 | 河北师范大学 | Method for preparing metal-doped lithium iron phosphate as cathode material of lithium ion battery |
| CN102642820A (en) * | 2012-03-29 | 2012-08-22 | 天津巴莫科技股份有限公司 | Preparation method of high-density spherical lithium iron phosphate |
| CN102751493A (en) * | 2012-06-27 | 2012-10-24 | 武陟县鑫凯科技材料有限公司 | Preparation method of lithium iron phosphate |
| CN102738454B (en) * | 2012-07-19 | 2015-04-29 | 北大先行科技产业有限公司 | Surface coating material for cathode material of lithium ion battery and preparation method |
| CN103840146A (en) * | 2012-11-27 | 2014-06-04 | 西安物华新能源科技有限公司 | Preparation method of high-tap-density lithium titanate material |
| CN103022462B (en) * | 2012-12-20 | 2015-07-08 | 中国东方电气集团有限公司 | Preparation method for high-conductivity lithium titanate cathode material of lithium battery |
| CN104752694A (en) * | 2013-12-30 | 2015-07-01 | 北京有色金属研究总院 | Improvement method for low temperature electrochemical performance of LiFePO4 material |
| CN105489824A (en) * | 2015-11-28 | 2016-04-13 | 芜湖迈特电子科技有限公司 | Quick-charging portable power source using lithium titanate battery |
| CN105870436A (en) * | 2016-04-25 | 2016-08-17 | 何凤英 | Preparation method of lithium titanate negative electrode material for lithium ion battery |
| CN109713299A (en) * | 2018-11-07 | 2019-05-03 | 贵州唯特高新能源科技有限公司 | A kind of preparation method of metal oxide Uniform Doped battery-grade iron phosphate |
| CN109659509A (en) * | 2018-11-07 | 2019-04-19 | 贵州唯特高新能源科技有限公司 | A kind of titanium dioxide uniformly coats the preparation method of battery-grade iron phosphate |
| CN109599547B (en) * | 2018-12-07 | 2022-05-13 | 天津市贝特瑞新能源科技有限公司 | NaTi2(PO4)3-TiO2Preparation method and application of/C composite electrode material |
| CN110550615B (en) * | 2019-10-14 | 2020-12-15 | 王敏 | Preparation method of high-energy-density lithium iron phosphate |
| CN111170294A (en) * | 2020-01-19 | 2020-05-19 | 江苏乐能电池股份有限公司 | Preparation method of low-cost lithium iron phosphate composite material |
| CN111403732B (en) * | 2020-03-30 | 2021-07-02 | 江西安驰新能源科技有限公司 | High-energy-density lithium iron phosphate battery |
| CN111740101B (en) * | 2020-06-17 | 2022-07-08 | 东莞东阳光科研发有限公司 | Lithium iron phosphate material and preparation method thereof |
| CN112713272B (en) * | 2020-12-18 | 2022-11-18 | 浙江金鹰瓦力新能源科技有限公司 | Preparation method of modified lithium battery positive electrode material |
| CN114759178A (en) * | 2022-04-25 | 2022-07-15 | 湖北万润新能源科技股份有限公司 | High-compaction lithium iron phosphate positive electrode material, preparation method thereof, positive electrode and battery |
| CN115259128B (en) * | 2022-08-05 | 2023-10-13 | 湖北融通高科先进材料集团股份有限公司 | Preparation method of high-compaction high-capacity low-cost lithium iron phosphate |
| CN115477296A (en) * | 2022-09-30 | 2022-12-16 | 欧赛新能源科技股份有限公司 | Method for preparing high-rate titanium-doped lithium iron phosphate by one-step process |
| CN116387496B (en) * | 2023-06-02 | 2023-10-31 | 瑞浦兰钧能源股份有限公司 | Secondary battery positive electrode material, secondary battery positive electrode plate and secondary battery |
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| CN101580238A (en) * | 2009-06-21 | 2009-11-18 | 海特电子集团有限公司 | Method for manufacturing composite lithium iron phosphate material and composite lithium iron phosphate material manufactured thereof |
| CN101635350A (en) * | 2009-08-31 | 2010-01-27 | 北京理工大学 | Preparation method of LiFePO4 of positive material of lithium ion battery |
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| CN101580238A (en) * | 2009-06-21 | 2009-11-18 | 海特电子集团有限公司 | Method for manufacturing composite lithium iron phosphate material and composite lithium iron phosphate material manufactured thereof |
| CN101635350A (en) * | 2009-08-31 | 2010-01-27 | 北京理工大学 | Preparation method of LiFePO4 of positive material of lithium ion battery |
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